KR20140119935A - Etching composition for copper-based metal layer and metal oxide layer and method of preparing metal line - Google Patents

Abstract

The present invention relates to an etching solution composition for a cooper-based metal film and a metal oxide film, and a method to form wirings using the same. More specifically, the etching solution includes: 0.5-20 wt% of persulfate, 0.01-1.0 wt% of a compound containing fluoride, 0.1-5 wt% of an azole compound, 1.0-5.0 wt% of sulfonic acid or salt thereof, 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 and a metal oxide film etchant composition, and a wiring forming method using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a copper-based metal film and a metal oxide film etchant composition capable of forming an excellent taper 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 Publication No. 2010-0040352 discloses an etching solution for selectively etching a copper or copper alloy layer containing hydrogen peroxide, phosphoric acid, a phosphate, a chelating agent, and a cyclic amine compound. However, in the case of the above patent, since the use of the copper or the copper alloy layer for etching other layers is completely excluded, its application range is very narrow.

Patent Document 1: Korean Patent Publication No. 2010-0040352

An object of the present invention is to provide an etchant composition capable of collectively etching a copper-based metal film and a metal oxide film.

Another object of the present invention is to provide an etchant composition capable of forming a taper profile having excellent linearity.

It is still another object of the present invention to provide an etchant composition which does not leave residues.

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 and a metal oxide film comprising 5 to 20 wt% of persulfate, 0.01 to 1.0 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 1.0 to 5.0 wt% of a sulfonic acid or a salt thereof, Film batch etchant composition.

2. The method of claim 1, wherein the persulfate comprises potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) Wherein at least one of the copper-based metal film and the metal oxide film is etched.

3. The method of 1 above, wherein the fluorine-containing compound is ammonium fluoride _{(ammonium fluoride: NH 4 F)} , sodium fluoride (sodium fluoride: NaF), potassium fluoride (potassium fluoride: KF), medium heat screen ammonium (ammonium bifluoride: NH ₄ Wherein at least one selected from the group consisting of sodium fluoride, sodium fluoride, sodium fluoride, potassium fluoride, potassium fluoride, fluoroboric acid fluoride, sodium bifluoride and potassium bifluoride is used.

4. 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, and a metal oxide film.

5. The composition of claim 1 wherein said sulfonic acid is selected from the group consisting of amidosulfonic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, wherein at least one member selected from the group consisting of an acid, an acid, a benzenesulfonic acid, a sulfamic acid, and a polystyrene sulfonic acid is used.

6. The copper-based metal film and metal oxide film batch etching composition according to 1 above, wherein the salt of the sulfonic acid is at least one selected from the group consisting of potassium salt, sodium salt and ammonium salt of sulfonic acid.

7. The copper-based metal film according to 1 above, wherein said 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 selected from the group consisting of copper, cobalt and nickel.

8. The copper-based metal film according to claim 7, 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.

9. The method of claim 1, wherein the metal oxide film is selected from the group consisting of A _x B _y C _z O, where A, B and C are independently selected from the group consisting of zinc (Zn), titanium (Ti), cadmium (Cd), gallium Wherein x, y and z represent the ratios of the respective metals and are integers of not less than 0 or not less than 0. In the present invention, the metal is selected from the group consisting of tin (In), tin (Sn), hafnium (Hf), zirconium (Zr), and tantalum Wherein the metal oxide film and the metal oxide film are formed with a ternary or tetrahedral oxide represented by the following formula (1).

10. (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) a step of collectively etching the metal oxide film and the upper copper-based metal film using the etching liquid composition according to any one of 1 to 9 above.

11. The metal oxide film of claim 10, 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.

12. The conductive film of claim 10, 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.

13. The copper-based metal film according to 12 above, 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.

14. 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 d), a semiconductor layer is formed of a metal oxide film, and a copper layer is formed on the semiconductor layer. And forming source and drain wirings by collectively etching the metal oxide film and the copper-based metal film with the etching liquid composition of any one of claims 1 to 9 after forming the metal film.

The etching solution composition of the present invention can collectively etch a copper-based metal film and a metal oxide film thereunder.

In addition, the etchant composition of the present invention exhibits a tapered profile having an excellent linearity in the etched pattern, and is excellent in preventing the formation of residues of the copper-based metal film and the metal oxide film, and thus has an excellent effect of preventing electrical shorts, poor wiring, .

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.

1 is a photograph showing an etched profile of a Cu / ITO double-layer film etched using the etchant composition of Example 4. FIG.
2 is a photograph showing the straightness of a Cu / ITO double layer etched using the etchant composition of Example 4. Fig.
3 is a photograph showing the etch profile of a Cu / Mo-Ti bilayer etched using the etchant composition of Example 4. FIG.
4 is a photograph showing the straightness of a Cu / Mo-Ti double layer etched using the etchant composition of Example 4. FIG.
5 is a photograph showing the etching profile of a Cu / ITO double layer etched using the etchant composition of Comparative Example 2. Fig.
6 is a photograph showing the straightness of a Cu / ITO double layer etched using the etchant composition of Comparative Example 2. Fig.
7 is a photograph showing the etching profile of a Cu / Mo-Ti double layer etched using the etchant composition of Comparative Example 2. Fig.
8 is a photograph showing the straightness of a Cu / Mo-Ti double layer etched using the etchant composition of Comparative Example 2. Fig.

The present invention includes a water repellent composition comprising 5-20 wt% of persulfate, 0.01-1.0 wt% of a fluorine-containing compound, 0.1-5 wt% of an azole compound, 0.5-5 wt% of a sulfonic acid or a salt thereof, The present invention relates to a copper-based metal film and a metal oxide film batch etchant composition having excellent taper profiles, and a wiring forming method using the same.

Hereinafter, the present invention will be described in detail.

The etching solution composition of the present invention is a composition for collectively etching a copper-based metal film and a metal oxide film, including a persulfate, a fluorine-containing compound, an azole compound, a sulfonic acid or a salt thereof, 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.

For example, A _x B _y C _z O (where A, B, and C are the same or different from each other) may be used as the metal oxide film in the present invention, (Zn), titanium (Ti), cadmium (Cd), gallium (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum And x, y and z represent the ratio of the respective metals, and are integers or prime numbers of 0 or more).

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 5 to 20 wt%, preferably 7 to 17 wt%, based on the total weight of the composition. If the content is less than 5% by weight, the etching rate is reduced and sufficient etching is not performed. If the content is more than 20% by weight, the etching rate is entirely accelerated, so that it is difficult to control the etching degree and over-etching occurs.

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 fluorine-containing compound contained in the etchant composition of the present invention means a compound capable of dissociating from water to emit fluoride ions. The fluorine-containing compound is a main component that etches the metal oxide film and serves to remove residues that are inevitably generated in a solution that simultaneously etches the copper-based metal film and the metal oxide film.

The fluorine-containing compound may be contained in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.2% by weight, based on the total amount of the composition. When the content is less than 0.01% by weight, etch residues are generated. When the content is more than 1.0% by weight, the etching rate of other layers such as a substrate becomes large.

Specific examples of the fluorine-containing compound include ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF) At least one selected from the group consisting of sodium bifluoride (NaF.HF) and potassium bifluoride (KF.HF).

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 1.5% 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 sulfonic acid or its salt contained in the etchant composition of the present invention dissociates (RSO ₃ H? ^- ? RSO ₃ ^- + H ⁺ ) in an aqueous solution and exhibits properties as an acid. The acidity of sulfonic acid is much stronger than that of carboxylic acids such as acetic acid, and is almost similar to that of sulfuric acid. In the etchant composition of the present invention, the pH of the etchant is controlled to increase the activity of the persulfate, thereby controlling the etching rate of the copper-based metal film and the metal oxide film and suppressing the decomposition reaction of the persulfate, It serves to lower the angle. In the present invention, the sulfonic acid generally refers to a compound having -SO ₃ H, and includes both an inorganic sulfonic acid and an organic sulfonic acid

The sulfonic acid or its salt may be contained in an amount of 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the total amount of the composition. If the content is less than 0.5% by weight, the pH control effect is not so large, and the etching rate of copper is lowered. If the content is more than 5.0% by weight, the etching rate may become too high, which may make process control difficult.

Specific examples of the sulfonic acid or its salt include sulfonic acids such as amidosulfonic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, at least one member selected from the group consisting of acid, benzenesulfonic acid, sulfamic acid, and polystyrene sulfonic acid. The salt of the sulfonic acid may be at least one selected from the group consisting of potassium salt, sodium salt and ammonium salt.

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 etchant composition of the present invention can be advantageously used for wiring formation because the etchant composition of the present invention etches the copper-based metal film and the metal oxide film in a batch and forms a taper profile with 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) collectively etching the metal oxide film and the copper-based metal film using the etching composition of the present invention.

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.

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, a molybdenum film or the above-described copper-based metal film can be used. The molybdenum film or the copper-based metal film may be patterned by photolithography or the like to form a gate wiring.

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 may be used.

Therefore, source and drain wiring can be formed by collectively etching the metal oxide film and the copper-based metal film in a desired pattern with the etchant composition according to the present invention.

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 9 and Comparative Examples 1 to 7 were prepared according to the composition shown in Table 1 below (unit: wt% (100 wt% in total)).

Persulfate Fluorine compound Azole compound Sulfonic acid (salt) Deionized water Kinds content Kinds content Kinds content Example 1 10.0 F-1 0.3 A-1 0.5 B-1 1.0 Balance Example 2 10.0 F-1 0.25 A-1 0.5 B-1 1.5 Balance Example 3 10.0 F-1 0.20 A-1 1.0 B-1 1.7 Balance Example 4 10.0 F-1 0.15 A-1 1.0 B-1 2.0 Balance Example 5 10.0 F-1 0.10 A-1 1.0 B-1 2.5 Balance Example 6 17.0 F-1 0.05 A-1 1.2 B-1 3.0 Balance Example 7 10.0 F-2 0.50 A-1 1.0 B-1 2.0 Balance Example 8 10.0 F-1 0.10 A-2 4.0 B-1 2.0 Balance Example 9 10.0 F-1 0.10 A-1 1.0 B-2 2.0 Balance Comparative Example 1 0.5 F-1 0.15 A-1 0.8 B-1 2.0 Balance Comparative Example 2 30.0 F-1 0.15 A-1 0.8 B-1 1.0 Balance Comparative Example 3 11.0 F-2 1.3 A-1 1.0 B-1 2.0 Balance Comparative Example 4 11.0 F-1 0.20 A-1 0.05 B-1 2.0 Balance Comparative Example 5 11.0 F-1 0.20 A-1 8 B-1 2.0 Balance Comparative Example 6 11.0 F-1 0.20 A-1 1.0 B-1 0.2 Balance Comparative Example 7 11.0 F-1 0.20 A-1 1.0 B-1 5.5 Balance
F-1: NH ₄ F
F-2: KF
A-1: Aminotetrazole
A-2: 1,2,4-triazole
B-1: Para-toluenesulfonic acid (PTSA)
B-2: Methanesulfonic acid

Test Example  One: Cu / ITO membrane Batch etching

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. And the compositions of Comparative Examples 1 to 7 were used to etch Cu / ITO bilayers, respectively.

(ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 30 캜 in the etching process. The etching time was about 100 seconds. The profile of the Cu / ITO double layer etched in the etching process was examined using a cross-sectional SEM (product of Hitachi, model name S-4700), and the results are shown in Table 2 below.

Test Example  2: Cu / Mo - Ti membrane Etching

A Mo-Ti film was deposited on a glass substrate (100 mm x 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. And the compositions of Comparative Examples 1 to 7 were used, respectively, to etch the Cu / Mo-Ti bilayers.

(ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 30 캜 in the etching process. The etching time was about 100 seconds. The profile of the Cu / Mo-Ti bilayer etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, Model S-4700) and the results are shown in Table 2 below.

< Etching  Profile evaluation criteria>

&Amp; cir &amp;: Taper angle was 35 DEG or more to less than 60 DEG

DELTA: Taper angle is 30 DEG or more to less than 35 DEG or 60 DEG or more to 65 DEG or less

Х: taper angle less than 30 ° or more than 65 °

Unetch: not etched

< Etching  Straightness evaluation standard>

○: The pattern is formed as a straight line

△: Pattern has less than 20% curved shape

Х: Over 20% curved pattern and undercut (erosion between Cu film and Cu film)

Unetch: not etched

Etching profile Etching straightness Temperature at addition of 3000 ppm of copper (캜) Cu / Mo-Ti Cu / ITO Cu / Mo-Ti Cu / ITO Early maximum Example 1 ○ ○ ○ ○ 31.2 35.0 Example 2 ○ ○ ○ ○ 31.0 34.8 Example 3 ○ ○ ○ ○ 30.7 34.5 Example 4 ○ ○ ○ ○ 30.4 34.0 Example 5 ○ ○ ○ ○ 30.0 34.0 Example 6 ○ ○ ○ ○ 29.5 32.4 Example 7 ○ ○ ○ ○ 30.0 34.1 Example 8 ○ ○ ○ ○ 30.1 33.4 Example 9 ○ ○ ○ ○ 30.0 34.2 Comparative Example 1 Cu Unetch Cu Unetch Cu Unetch Cu Unetch 31.2 34.5 Comparative Example 2 X
(pattern out) X
(pattern out) X
(pattern out) X
(pattern out) 28.5 32.3 Comparative Example 3 X X X X 30.5 34.2 Comparative Example 4 X
(pattern out) X
(pattern out) X
(pattern out) X
(pattern out) 29.8 34.3 Comparative Example 5 Cu Unetch Cu Unetch Cu Unetch Cu Unetch 29.5 34.2 Comparative Example 6 Cu Unetch Cu Unetch Cu Unetch Cu Unetch 29.8 35.1 Comparative Example 7 X
(pattern out) X
(pattern out) X
(pattern out) X
(pattern out) 29.6 32.5

As shown in Table 2, the etching solution compositions of Examples 1 to 9 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. In Comparative Example 2 in which persulfate was excessively contained, a pattern out phenomenon And - etching) were found to be incompatible with the etchant composition. The undercut phenomenon occurred in the case of the etching solution of Comparative Example 3 in which the fluorine-containing compound was added in excess. In Comparative Example 4 in which a small amount of an azole compound was contained, pattern out occurred due to a rapid etching rate. In Comparative Example 5, which was added in an excess amount, unetching occurred because the etching rate was too slow. In Comparative Example 6 in which a small amount of sulfonic acid was contained, unetching phenomenon occurred because the etching rate was too slow, and pattern out phenomenon occurred in Comparative Example 7 in which excess was included.

In addition, it was confirmed that when 3000 ppm of Cu eluted, the superheat stability characteristics of the etchant were improved as the sulfonic acid content was increased to 35.0 ° C and 3.0% (Example 6) at 1.0% sulfonic acid content (Example 6) and 32.4 ° C, respectively.

1 and 3, it was confirmed that the Cu / ITO double layer and the Cu / Mo-Ti double layer etched with the etchant composition according to Example 4 exhibited a good taper profile. Referring to FIGS. 2 and 4, it can be seen that the straightness of the Cu / ITO double layer and the Cu / Mo-Ti double layer etched by the etchant composition according to Example 4 is excellent and the etching residue is not left.

On the other hand, as can be seen from FIGS. 5 to 8, the copper-based metal film etched with the etchant composition according to Comparative Example 1 exhibited a phenomenon in which copper was not etched.

Claims (14)

A copper-based metal film and a metal oxide film containing 5 to 20 wt% of persulfate, 0.01 to 1.0 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.5 to 5.0 wt% of a sulfonic acid or a salt thereof, Etchant composition.
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 ) Wherein at least one selected from the group consisting of ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) and a metal oxide film are provided.
The method of claim 1, wherein the fluorine-containing compound is selected from the group consisting of ammonium fluoride (NH4F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH4F.HF) Wherein at least one selected from the group consisting of sodium bifluoride (NaF 占 HF) and potassium bifluoride (KF 占 HF) is used.
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 metal oxide film.
The method of claim 1, wherein the sulfonic acid is selected from the group consisting of amidosulfonic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, Wherein at least one member selected from the group consisting of benzenesulfonic acid, sulfamic acid, and polystyrene sulfonic acid is used as the etching solution.
The copper-based metal film and metal oxide film batch etching solution composition according to claim 1, wherein the salt of the sulfonic acid is at least one selected from the group consisting of a potassium salt, a sodium salt and an ammonium salt of a sulfonic acid.
[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 7, 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.
The metal oxide film according to claim 1, wherein the metal oxide film comprises A _x B _y C _z O, where 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, ) And a ternary or tetravalent oxide represented by the following formula (1).
(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) A method for forming a wiring comprising a step of collectively etching the metal oxide film and the copper-based metal film using the etching liquid composition according to any one of claims 1 to 9.
11. The method of claim 10, wherein the metal oxide layer is formed of a material selected from the group consisting of A _x B _y C _z O (where 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.
11. The method of claim 10, 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 12, 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:
In the step d), a semiconductor layer is formed of a metal oxide film, a copper-based metal film is formed on the semiconductor layer, and the metal oxide film and the copper-based metal film are etched by batch etching using the etching solution composition of any one of claims 1 to 9 And forming a source and a drain wiring.

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