KR20140119885A - Etching composition for copper-based metal layer and method of preparing metal line - Google Patents

Abstract

The present invention relates to an etching solution composition for a copper-based metal film and a method for forming wiring using the same. More specifically, the etching solution includes: 0.5-20 wt% of persulfate, 0.1-5 wt% of azole compound, 0.5-3 wt% of salt of copper, and the remainder consisting of water. The etching composition selectively etches only the copper-based metal film and has a taper profile with excellent straightness of an etched pattern.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper-based metal film etchant composition and a wiring forming method using the same. BACKGROUND ART [0002]

The present invention relates to a copper-based metal film etchant composition capable of forming an excellent tapered profile and a method of forming a wiring using the same.

A typical semiconductor-related device to which low resistance wiring including copper is applied is a liquid crystal display (LCD).

The liquid crystal display, which is a lightweight thin film flat panel display (FPD) replacing a conventional cathode ray tube (CRT) as a display device, is an apparatus for displaying an image using optical anisotropy of a liquid crystal, Color display and picture quality, and is being actively applied to a notebook or a desktop monitor.

The liquid crystal display comprises a color filter substrate, an array substrate, and a liquid crystal layer formed between the color filter substrate and the array substrate.

An active matrix (AM) method, which is a driving method mainly used in the liquid crystal display, is a method of driving a liquid crystal of a pixel portion by using an amorphous silicon thin film transistor (a-Si TFT) to be.

In such a liquid crystal display device, a material forming a metal wiring such as a gate line or a data line serving as a signal mediator can increase the reliability and price competitiveness of a product as the selection is made from a metal having a low specific resistance and a high corrosion resistance. Aluminum (Al) or aluminum alloy (Al alloy) has been mainly used as the metal wiring material.

However, as the resolution becomes higher due to the large size and SVGA, XGA, SXGA, VXGA, etc., the scanning time is shortened and the signal processing speed is increased. Therefore, it is inevitable to form a metal wiring with a low resistance metal material .

Recently, copper has been actively proposed as a substitute for copper, which has better resistivity and electromigration characteristics than conventional metal wiring materials.

Under such circumstances, there is a high interest in the etching solution composition of a copper film or a copper-based metal film as a new low-resistance metal film. However, in the case of the etching solution composition for the copper-based metal film, various kinds are currently used, but the performance required by users is not satisfied.

For example, Korean Patent Laid-Open Publication No. 2005-0067934 discloses an etchant for collectively etching a copper metal layer containing nitric acid, hydrochloric acid, hydrogen peroxide, and an azole compound and a transparent conductive layer. However, the above-mentioned patent has a problem that not only the upper copper film but also the indium oxide film as the lower film is etched.

Korea Patent Publication No. 2005-0067934

An object of the present invention is to provide a copper-based metal film etchant composition capable of forming a taper profile having excellent linearity.

Another object of the present invention is to provide an etchant composition for a copper-based metal film in which a residue of a copper-based metal film is not left.

It is still another object of the present invention to provide a method of forming a wiring using the etchant composition.

1. A copper-based metal film etchant composition comprising 0.5 to 20 wt% persulfate, 0.1 to 5 wt% of an azole compound, 0.5 to 3 wt% of a copper salt, and a balance of water.

2. The method of claim 1, wherein the persulfate is potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) And And ammonium sulfate _{((NH 4) 2 S 2} O 8) is selected from the group consisting of at least one kind of copper-based metal film etching liquid composition.

3. The azole compound according to item 1, wherein the azole compound is at least one compound selected from the group consisting of a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, A pyrrolidine-based compound, and a pyrroline-based compound.

4. The copper-based metal film etchant composition according to 1 above, wherein the copper salt is at least one selected from the group consisting of copper sulfate, copper nitrate, copper chloride, copper acetate and copper fluoride.

5. The copper-based metal film according to item 1, wherein the copper-based metal film is at least one selected from the group consisting of copper, a nitride of copper, and an oxide of copper; (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and at least one member selected from the group consisting of copper, Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten Wherein the copper-based metal-film etchant composition comprises an alloy of at least one metal selected from the group consisting of copper and tin.

6. The copper-based metal film according to claim 5, wherein the copper-based metal film comprises a copper-molybdenum film or a molybdenum alloy layer including a molybdenum layer and the copper-based metal film formed on the molybdenum layer and the copper-based metal film formed on the molybdenum alloy layer Wherein the copper-molybdenum alloy film contains a copper-molybdenum alloy film.

7. (S1) forming a metal oxide film on a substrate; (S2) forming a copper-based metal film on the metal oxide film; (S3) selectively forming a photoresist pattern on the copper-based metal film; And (S4) etching the copper-based metal film on the metal oxide film using the etching liquid composition according to any one of (1) to (6) above.

8. The metal oxide film of claim 7, wherein the metal oxide film is selected from the group consisting of AxByCzO wherein A, B and C are independently selected from the group consisting of zinc (Zn), titanium (Ti), cadmium (Cd), gallium (Ga), indium (In) ), Hafnium (Hf), zirconium (Zr) and tantalum (Ta), x, y and z represent the ratios of the respective metals, Ternary or tetra-component oxide.

9. The copper-based metal film according to claim 7, wherein the copper-based metal film is at least one selected from the group consisting of copper, a nitride of copper, and an oxide of copper; (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and at least one member selected from the group consisting of copper, Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten And at least one kind of metal.

10. The copper-based metal film according to claim 9, wherein the copper-based metal film comprises a copper-molybdenum film or a molybdenum alloy layer including a molybdenum layer and the copper-based metal film formed on the molybdenum layer and the copper-based metal film formed on the molybdenum alloy layer Wherein the copper-molybdenum alloy film comprises a copper-molybdenum alloy film.

11. A method comprising: a) forming a gate wiring on a 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 a source and a drain wiring on the semiconductor layer; And e) forming a pixel electrode connected to the drain wiring. In the step a), a copper-based metal film is formed on the substrate, And etching the copper-based metal film with the etching solution composition to form a gate wiring.

12. A method comprising: a) forming a gate wiring on a 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 a source and a drain wiring on the semiconductor layer; And e) forming a pixel electrode connected to the drain wiring, wherein the step d) comprises forming a copper-based metal film and forming an etchant composition according to any one of items 1 to 6 above And etching the copper-based metal film to form source and drain wirings.

The etching solution composition of the present invention can selectively etch only the copper-based metal film without etching the metal oxide film under the copper-based metal film.

In addition, the etchant composition of the present invention exhibits a tapered profile with excellent linearity in the etched pattern, and has an excellent effect of preventing electrical shorts, wiring defects, luminance reduction, and the like because it has an excellent effect of preventing residue formation of the copper-

Since the wiring forming method of the present invention is a wet etching method, not a dry etching method, expensive equipment and the like are not required, which is economical.

The present invention relates to a process for selectively etching only a copper-based metal film by containing 0.5 to 20 wt% of persulfate, 0.1 to 5 wt% of an azole compound, 0.5 to 3 wt% of a copper salt, The present invention relates to a copper-based metal film etchant composition having an excellent taper profile and a wiring forming method using the same.

Hereinafter, the present invention will be described in detail.

The etchant composition of the present invention is a composition for etching a copper-based metal film, including a persulfate, an azole compound, a copper salt, and a residual amount of water.

In the present invention, the copper-based metal film is a film used as a raw material for forming a metal wiring for transmitting an electric signal, and refers to a metal film including copper. The copper-based metal film to which the etchant of the present invention can be applied is not particularly limited as long as it is a concept including a single film or a multilayer film and is a copper-based metal film conforming to the above definition. Examples thereof include copper, a nitride of copper, At least one member selected from the group consisting of: (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and at least one member selected from the group consisting of copper, Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten But not limited to, a metal film formed of an alloy of at least one kind of metal.

Further, the copper-based metal film is a concept including a multilayer film such as a single film and a double film. A single film of the above-mentioned copper-based metal film, or a copper-molybdenum film or a copper-molybdenum alloy film as a multilayer film. Wherein the copper-molybdenum film comprises a molybdenum layer and the copper-based metal film formed on the molybdenum layer, wherein the copper-molybdenum alloy film includes a molybdenum alloy layer and the copper-based metal film formed on the molybdenum alloy layer it means. The molybdenum alloy may be an alloy of molybdenum and at least one metal selected from the group consisting of Ti, Ta, Cr, Ni, Nd and In.

The persulfate contained in the etchant composition of the present invention is the main component for etching the copper-based metal film. The persulfate is included in an amount of 0.5 to 20 wt%, preferably 1 to 15 wt%, based on the total weight of the composition. When the content is less than 0.5% by weight, the etching rate is decreased and sufficient etching is not performed. If the content is more than 20% by weight, the etching rate is generally accelerated, so that it is difficult to control the etching degree and the copper- .

The persulfate usable in the present invention is not particularly limited, and examples thereof include potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) may be used alone or in combination of two or more.

The azole compound included in the etchant composition of the present invention controls the etching rate and reduces the CD loss of the pattern, thereby enhancing the process margin. The content of the azole compound may be 0.1 to 5% by weight, preferably 0.5 to 2% by weight based on the total weight of the composition. If the content is less than 0.1% by weight, the CD loss may be excessively large. If the content is more than 5% by weight, the etching time of the copper-based metal film becomes too slow, and thus the process time becomes excessively long.

The azole compound can be used without any particular limitation as long as it is used in the art. For example, the azole compound is preferably an azole compound having 1 to 30 carbon atoms. More preferably, it is a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole-based compound, a purine-based compound, a pyrazole-based compound, a pyridine-based compound, a pyrimidine- And the like may be used alone or in combination of two or more.

As the triazole-based compound, for example, compounds represented by the following formula (1) may be used alone or in combination of two or more.

[Chemical Formula 1]

(Wherein R ¹ and R ² are independently of each other a hydrogen atom, a carboxyl group, an amino group, a hydroxy group, a cyano group, a formyl group, a sulfo group, a carboxyl group, an amino group, a hydroxy group, a cyano group, An alkyl or sulfonylalkyl group having 1 to 20 carbon atoms, which may contain an ester group,

Q is a hydrogen atom; A hydroxy group; A substituent represented by the following formula (2); An aryl group having 6 to 20 carbon atoms or an alkyl or alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group and may include at least one of an amide group and an ester group)

(2)

(Wherein R ³ is an alkylene group having 1 to 6 carbon atoms;

R ⁴ and R ⁵ are independently of each other a hydrogen atom, a hydroxy group, or an alkyl, hydroxyalkyl or alkoxyalkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group.

Examples of the compound represented by Formula 1 include 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1- (2,2-dihydroxyethyl) benzotriazole, 1 (1, 2-dihydroxypropyl) benzotriazole, 1- (2,3-dihydroxypropyl) benzotriazole, N, N (2-ethylhexyl) -arylmethyl-1H-benzotriazole-1-methanamine {N, N-BIS- (2-ETHYLHEXYL) -ARYLMETHYL-1H-BENZOTRIAZOLE-1-METHANAMINE} Benzo [b] thiazol-1-yl) methyl] imino} bisethanol and 2,2 '- {[(5-methyl- ] Imino} bisethanol, 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, 5-carboxybenzotriazole dodecyl ester, and the like. These may be used alone or in combination of two or more.

The present invention may further include a triazole-based compound commonly used in the art in addition to the compound represented by the formula (1), for example, 1,2,3-triazole, 1,2,4-triazole, Triazole, 4-amino-1,2,4-triazole, and the like. These may be used alone or in combination of two or more.

Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propimidazole, 2-aminoimidazole, , And 4-propylimidazole may be used alone or in combination of two or more.

Examples of the aminotetrazole compound include aminotetrazole, 5-aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino- Aminotetrazole, 5-aminotetrazole, 1,5-diaminotetrazole, and the like, preferably aminotetrazole.

As the indole-based compound, aminoalkylindole, benzoylindole, methylindole, phenylacetylindole, indolecarbazole, etc. may be used alone or in combination of two or more.

Examples of the purine compound include 6-dimethylaminopurine, 2,6-dichloro-7-methyl-7H-purine, 6- (?,? -Dimethylallylamino) 9-acetic acid and the like can be used singly or in combination of two or more.

Examples of the pyrazole-based compound include 3-phenyl-1H-pyrazole, 3- (aminomethyl) pyrazole, 5- (2-cyanyl) pyrazole, 1- Pyrazole, 5-methyl-1H-pyrazole, 4-nitro-1H-pyrazole, 1H-pyrazole-5-boronic acid, They may be used alone or in combination of two or more.

Examples of the pyridine compound include 4- (aminoethyl) pyridine, 2- (methylamino) pyridine, pyridine trifluoroacetate, pyridine- -Benzoic acid may be used alone or in combination of two or more.

As the pyrimidine-based compound, pyrimidine-5-carboxylic acid, pyrimidine-2-carboxylic acid, etc. may be used each alone or in combination of two or more.

Examples of the pyrrole compound include pyrrole-2-carboxylic acid, pyrrole-3-carboxylic acid, 1- (2-aminophenyl) pyrrole, Can be used.

Examples of the pyrrolidine-based compound include 1- (2-aminoethyl) pyrrolidine, pyrrolidine-3-carboxylic acid, pyrrolidine-3-carboxylic acid hydrochloride, pyrrolidine- 2-dicarboxylic acid 1-phenyl ester, and the like, or a mixture of two or more thereof.

As the pyrroline compound, 3-pyrroline, 2-methyl-1-pyrroline, 1-benzyl-3-pyrroline and the like may be used either singly or as a mixture of two or more thereof.

The copper salt contained in the etchant composition of the present invention controls the CD skew by controlling the etching rate of the copper-based metal film by adjusting the pH of the etchant to increase the activity of the persulfate, And also serves to lower the taper angle of the etched surface.

The copper salt may be contained in an amount of 0.5 to 3% by weight, preferably 1 to 2% by weight, based on the total amount of the composition. If the content is less than 0.5% by weight, a change in CD skew by the number of treatments is marked. If the content is more than 3% by weight, the oxidizing power of the peroxide is reduced and the number of treatments is decreased .

Specific examples of the copper salt may be at least one selected from the group consisting of copper sulfate, copper nitrate, copper chloride, copper acetate and copper fluoride.

In the etchant composition of the present invention, water is included as the balance other than the content of the components 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. Further, it is more preferable to use deionized water having a specific resistance of water of 18 M OMEGA. Or more to show the degree of removal of ions in water.

Alternatively, the etchant composition of the present invention may further comprise a surfactant. The surfactant serves to lower the surface tension and increase the uniformity of the etching. The surfactant is not particularly limited as long as it can withstand the etching composition of the present invention and is compatible with the surfactant. However, the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and a polyhydric alcohol surfactant , Or a combination thereof.

In the etchant composition of the present invention, conventional additives may be further added in addition to the above-mentioned components, and examples thereof include a metal ion sequestering agent and a corrosion inhibitor.

The copper-based metal film etchant composition of the present invention can be advantageously used for wiring formation by selectively etching a copper-based metal film and forming a taper profile having excellent linearity.

One embodiment of the wiring formation method of the present invention comprises: (S1) forming a metal oxide film on a substrate; (S2) forming a copper-based metal film on the metal oxide film; (S3) selectively forming a photoresist pattern on the copper-based metal film; And (S4) etching only the copper-based metal film on the metal oxide film using the etching liquid composition of any one of claims 1 to 5. [

In the wiring formation method of the present invention, the photosensitive pattern may be formed by a conventional photoresist, and may be formed by a conventional exposure and development process.

In the wiring forming method of the present invention, the metal oxide film can be a film which can form an oxide semiconductor layer, and a metal oxide film commonly used in the art can be used. For example, A _x B _y C _z O (A, B and C are independently selected from the group consisting of Zn, Ti, Cd, Ga, In, Sn, Hf, Zr, ), And x, y and z represent the ratios of the respective metals, which may be an integer of 0 or more or a prime number), and may be ternary or quaternary oxides.

The wiring forming method of the present invention can be applied to the manufacture of an array substrate of a liquid crystal display device. The manufacturing method of the array substrate of the liquid crystal display device according to the present invention will now be described in more detail.

First, a gate wiring is formed on a substrate. The gate wiring functions to control the current between the source and the drain in accordance with an electrical signal transmitted through the gate line. As the material of the gate wiring, the above-described copper-based metal film can be used, so that the gate wiring can be formed by etching the copper-based metal film with a desired pattern with the etchant composition according to the present invention.

Next, a gate insulating layer is formed on the gate wiring. The gate insulating layer separates the active layer and the gate wiring from each other and functions to prevent a current flowing into the active layer from flowing into the gate wiring.

The gate insulating layer is formed as follows. That is, it is uniformly formed on a substrate including the gate wiring by a plasma chemical vapor deposition (CVD) method or the like. The gate insulating layer may be formed of an insulating material formed of at least one material from among silicon oxide (SiO _2), silicon nitride (SiNx), silicon oxynitride (SiONx).

Next, a semiconductor layer is formed on the gate insulating layer. The semiconductor layer becomes a current path in accordance with the electrical conduction of the gate wiring. The active layer can be uniformly formed on the gate insulating layer by a plasma CVD method or the like using amorphous silicon or the above-mentioned metal oxide (A _x B _y C _z O).

Next, source and drain wirings are formed on the semiconductor layer. The source wiring and the drain wiring serve to transmit an electrical signal to the pixel (pixel). As the material of the source and drain wirings, the above-described copper-based metal film can be used, and thus the source and drain wirings can be formed by etching the copper-based metal film with the etching composition according to the present invention in a desired pattern.

Next, a pixel electrode connected to the drain wiring is formed.

With this process, an array substrate for a liquid crystal display device can be manufactured.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  And Comparative Example

The etching solution compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were prepared according to the compositions shown in Table 1 below (unit: wt% (total 100 wt%)).

division Persulfate Azole compound Copper salt (salt) Deionized water Kinds content Kinds content Example 1 5 A-1 One B-1 One Balance Example 2 10 A-1 One B-1 2 Balance Example 3 15 A-1 One B-1 3 Balance Example 4 10 A-1 0.5 B-1 2 Balance Example 5 10 A-2 4 B-1 2 Balance Example 6 10 A-1 One B-2 2 Balance Comparative Example 1 0.3 A-1 One B-1 2 Balance Comparative Example 2 23 A-1 One B-1 2 Balance Comparative Example 3 10 A-1 0.05 B-1 2 Balance Comparative Example 4 10 A-2 8 B-1 2 Balance Comparative Example 5 10 A-2 One B-1 5 Balance Comparative Example 6 10 A-1 One B-1 0.1 Balance
A-1: Aminotetrazole
A-2: 1,2,3-benzotriazole
B-1: CuSO ₄
B-2: CuCl ₂

Test Example

A metal oxide (ITO) film was deposited on a glass substrate (100 mm × 100 mm), a copper film was deposited on the film, and a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. The copper-based metal film was subjected to an etching process using the compositions of Examples 1 to 6 and Comparative Examples 1 to 6, respectively.

(ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set at about 30 ° C. during the etching process. However, the optimum temperature was determined according to other process conditions and other factors can be changed. The etching time may vary depending on the etching temperature, but is usually about 100 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, model name S-4700), and the results are shown in Table 2 below.

< Etching  Profile evaluation criteria>

&Amp; cir &amp;: Taper angle was 35 DEG to 60 DEG

DELTA: The taper angle is less than 35 DEG to more than 60 DEG

Х: undercut or reverse-Taper

Unetch: not etched

< Etching  Straightness evaluation standard>

○: The pattern is formed as a straight line

△: Pattern has less than 20% curved shape

Х: Pattern has more than 20% curved shape

Unetch: not etched

division Etching profile Etching straightness Presence or absence of residue Metal oxide (ITO) film
Whether etched Example 1 ○ ○ radish none Example 2 ○ ○ radish none Example 3 ○ ○ radish none Example 4 ○ ○ radish none Example 5 ○ ○ radish none Example 6 ○ ○ radish none Comparative Example 1 Cu Unetch Cu Unetch U none Comparative Example 2 X X radish none Comparative Example 3 X X radish none Comparative Example 4 Cu Unetch Cu Unetch U none Comparative Example 5 △ △ radish none Comparative Example 6 △ △ radish none

As shown in Table 2, the etching solution compositions of Examples 1 to 6 all exhibited good etching properties.

However, in Comparative Example 1 in which the content of persulfate was less than the range of the present invention, etching of the copper film was not possible, and Comparative Example 2 in which persulfate was excessively contained was confirmed to be etched. In the case of the etchant of Comparative Example 3, it was confirmed that the content of the azole compound was too low to be etched. Further, in Comparative Example 4 in which an azole compound was contained in an excessive amount, etching of the copper film was not possible. In Comparative Example 5 in which copper salt was excessively added, the etching profile and straightness were not good, and in Comparative Example 6 in which a small amount of copper salt was added, the etching profile and straightness were not good due to the slow etching rate.

Claims (12)

0.5 to 20% by weight of persulfate, 0.1 to 5% by weight of an azole compound, 0.5 to 3% by weight of a copper salt, and a balance of water.
The method of claim 1, wherein the persulfate is selected from the group consisting of potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) And ammonium sulfate _{((NH 4) 2 S 2} O 8) is selected from the group consisting of at least one kind of copper-based metal film etching liquid composition.
The azole compound according to claim 1, wherein the azole compound is selected from the group consisting of a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole-based compound, a purine-based compound, a pyrazole-based compound, a pyridine-based compound, a pyrimidine- Based compound and at least one selected from the group consisting of a pyrrole-based compound and a pyrrole-based compound.
The copper-based metal film etchant composition of claim 1, wherein the copper salt is at least one selected from the group consisting of copper sulfate, copper nitrate, copper chloride, copper acetate and copper fluoride.
[2] The method of claim 1, wherein the copper-based metal film comprises at least one selected from the group consisting of copper, a nitride of copper, and an oxide of copper; (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and at least one member selected from the group consisting of copper, Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten And at least one kind of metal selected from the group consisting of copper and tin.
The copper-based metal film according to claim 5, wherein the copper-based metal film comprises a copper-molybdenum film or a molybdenum alloy layer including a molybdenum layer and the copper-based metal film formed on the molybdenum layer and the copper-based metal film formed on the molybdenum alloy layer Copper-molybdenum alloy film.
(S1) forming a metal oxide film on a substrate;
(S2) forming a copper-based metal film on the metal oxide film;
(S3) selectively forming a photoresist pattern on the copper-based metal film; And
(S4) etching the copper-based metal film on the metal oxide film using the etching liquid composition according to any one of claims 1 to 6;
[7] The method of claim 7, wherein the metal oxide layer comprises at least one selected from the group consisting of A _x B _y C _z O (A, B, and C are independently selected from the group consisting of zinc (Zn), titanium (Ti), cadmium (Cd), gallium (Ga) , Tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum (Ta), x, y and z represent the ratios of the respective metals, ) &Lt; / RTI &gt; oxide.
8. The method of claim 7, wherein the copper-based metal film comprises at least one selected from the group consisting of copper, a nitride of copper, and an oxide of copper; (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and at least one member selected from the group consisting of copper, Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten And at least one kind of metal.
The copper-based metal film according to claim 9, wherein the copper-based metal film comprises a copper-molybdenum film or a molybdenum alloy layer including a molybdenum layer and the copper-based metal film formed on the molybdenum layer and the copper-based metal film formed on the molybdenum alloy layer Copper-molybdenum alloy film.
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 a source and a drain wiring on the semiconductor layer; And
and e) forming a pixel electrode connected to the drain wiring, the method comprising the steps of:
Wherein the step a) is a step of forming a copper-based metal film on a substrate and etching the copper-based metal film with the etching liquid composition according to any one of claims 1 to 6 to form gate wirings.
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 a source and a drain wiring on the semiconductor layer; And
and e) forming a pixel electrode connected to the drain wiring, the method comprising the steps of:
Wherein the step d) comprises forming a copper-based metal film and etching the copper-based metal film with the etching liquid composition according to any one of claims 1 to 6 to form source and drain wirings.