KR20140108795A - Echaing composition for copper-based metal layer and multiful layer of 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 copper-based metal film and a film on which a cooper-based metal film and a metal oxide film are laminated, and a method for forming wirings using the same etching solution. The etching solution includes 15-25 wt% of hydrogen peroxide, 0.01-1.0 wt% of a compound containing fluoride, 0.1-1.0 wt% of an Azole compound, 0.5-5 wt% of a soluble compound having a nitrogen atom and a carboxyl group in one molecule; 0.5-3.0 wt% of glycolic acid, 0.5-3.0 wt% of organic acid except for glycolic acid, 0.1-2.0 wt% of nitric acid, sulfuric acid or salts thereof, 0.001-5.0 wt% of a polyhydric alcohol type surfactant, and the remainder consisting of water. The etching solution: selectively etches the cooper-based metal film; imposes excellent straightness on a pattern etched; and has an enhanced taper profile.

Description

TECHNICAL FIELD [0001] The present invention relates to an etching solution composition for a copper-based metal film, a copper-based metal film, and a metal oxide film, and a method for forming a wiring using the same. BACKGROUND ART LINE}

The present invention relates to a copper-based metal film capable of forming an excellent taper profile, and a laminated film etchant composition of a copper-based metal film and a metal oxide film.

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. 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

It is an object of the present invention to provide an etchant composition capable of etching not only a copper-based metal film but also a laminated film of a copper-based metal film and a metal oxide film.

Another object of the present invention is to provide an etchant composition which is excellent in straightness and can form an improved taper profile.

It is still another object of the present invention to provide an etchant composition in which formation of a tail is suppressed.

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

1. A water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, 0.5 to 5 wt% of a water-soluble compound, 0.5 to 3.0 wt% of a glycolic acid, 0.01 to 1.0 wt% of a fluorine-containing compound, 0.1 to 1.0 wt% 0.5 to 3.0% by weight of organic acid excluding glycolic acid, 0.1 to 2.0% by weight of nitric acid, sulfuric acid or its salt, 0.001 to 5.0% by weight of polyhydric alcohol type surfactant and water in the balance, and copper- And a metal oxide film.

2. In the above 1, 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 A copper-based metal film and a copper-based metal film, which are at least one kind selected from the group consisting of fluoride, fluoride, fluoride, sodium bifluoride (NaF.HF), and potassium bifluoride (KF.HF) Film laminate film etchant 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 copper-based metal film and a copper-based metal film and a metal oxide film, wherein the copper-based metal film is at least one selected from the group consisting of a pyrrolidine-based compound and a pyrroline-based compound.

4. The method of claim 1, wherein the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule is selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, A copper-based metal film and at least one selected from the group consisting of nitrilotriacetic acid, ethylenediamine tetraacetic acid, and sarcosine; and a laminated film etchant composition of a copper-based metal film and a metal oxide film .

5. The organic acid according to 1 above, wherein the organic acid excluding the glycolic acid is at least one selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, malonic acid, pentanoic acid, lactic acid and oxalic acid, A laminated film etchant composition comprising a copper-based metal film and a metal oxide film.

6. The method of claim 1, wherein the salt of nitric acid or sulfuric acid is at least one selected from the group consisting of potassium salt, calcium salt, sodium salt and ammonium salt of nitric acid or sulfuric acid, and a copper- Layer film etchant composition.

7. The composition of claim 1, wherein the polyhydric alcohol surfactant is at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol, and a copper- Film and a metal oxide film.

8. The copper-based metal film according to 1 above, 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 a copper-based metal film and a metal oxide film, wherein the copper-based metal film and the metal-based metal film are formed of an alloy of at least one metal selected from the group consisting of copper,

9. The copper-based metal film according to claim 8, 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-based metal film comprises a copper-molybdenum alloy film or a copper-titanium film including the copper-based metal film formed on the titanium layer, and a laminated film etchant composition of a copper-based metal film and a metal oxide film.

10. The metal oxide film of claim 1, wherein the metal oxide film comprises 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 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 A copper-based metal film, a copper-based metal film, and a metal oxide film, each of which is a film formed with a ternary or tetra-element oxide represented by the following formula:

11. (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 copper-based metal film using the etching liquid composition according to any one of 1 to 10 above.

12. The method of claim 11, wherein the metal oxide layer is selected from the group consisting of A _x B _y C _z O wherein 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 film is formed of a ternary or quaternary oxide represented by the following formula.

13. The conductive film of claim 11, 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.

14. The copper-based metal film according to claim 13, 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.

15. 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, the method comprising the steps of:

The step a) includes forming a metal film on the substrate, and then etching the metal film with the etching solution composition according to any one of [1] to [10] to form a gate wiring,

The step d) includes forming a metal film on the semiconductor layer, and then etching the metal film with the etching composition of any one of [1] to [10] to form a source and a drain wiring,

The metal film in the steps a) and d) is a copper-based metal film or a laminated film of a copper-based metal film and a metal oxide film,

Wherein the etchant of steps a) and d) is the same etchant.

16. 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, the method comprising the steps of:

In the step a), a copper-based metal film and a metal oxide film are formed on the substrate, and then the copper-based metal film and the metal oxide film are etched with the etchant composition according to any one of the above 1 to 10, ; And

The step d) includes forming a copper-based metal film on the semiconductor layer, and etching the copper-based metal film with the etchant composition according to any one of [1] to [10]

Wherein the etchant of steps a) and d) is the same etchant.

17. The method for manufacturing an array substrate for a liquid crystal display device according to 16 above, wherein the copper-based metal film in the step d) is a copper-molybdenum film or a copper-molybdenum alloy film.

The etchant composition of the present invention can etch not only a copper-based metal film but also a laminated film of a copper-based metal film and a metal oxide film. Therefore, in the production of a liquid crystal array substrate, it is an etchant composition which can be applied with the same composition for both formation of a gate wiring and formation of a source / drain wiring.

In addition, the etchant composition of the present invention is excellent in the straightness of the etched pattern, exhibits an improved taper profile, and has an excellent effect of preventing formation of tails of the copper-based metal film and the metal oxide film, great.

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.

FIG. 1 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of a Cu / Mo-Ti double film etched using the etching composition of Example 2. FIG.
FIG. 2 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of a Cu / ITO double film etched using the etching composition of Example 2. FIG.
3 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of a Cu / Mo-Ti double film etched using the etching composition of Comparative Example 1. FIG.
FIG. 4 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of a Cu / ITO double film etched using the etching composition of Comparative Example 1. FIG.
FIG. 5 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of a Cu / Mo-Ti double film etched using the etching composition of Comparative Example 2. FIG.
FIG. 6 is a photograph showing the etching taper profile (a), the etching straightness and the tail (b) of the Cu / ITO double film etched using the etching composition of Comparative Example 2. FIG.

The present invention relates to a water-soluble polymer comprising 15 to 25% by weight of hydrogen peroxide, 0.01 to 1.0% by weight of a fluorine-containing compound, 0.1 to 1.0% by weight of an azole compound, 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, By weight, 1.0 to 5.0% by weight of organic acid excluding glycolic acid, 0.1 to 2.0% by weight of nitric acid, sulfuric acid or its salt, 0.001 to 5.0% by weight of polyhydric alcohol type surfactant and water in the remaining amount, A copper-based metal film having an improved taper profile, and a laminated film etchant composition of a copper-based metal film and a metal oxide film.

Hereinafter, the present invention will be described in detail.

The etchant composition of the present invention comprises hydrogen peroxide; Fluorine-containing compounds; Azole compounds; A water-soluble compound having a nitrogen atom and a carboxyl group in one molecule; Glycolic acid; Organic acids other than glycolic acid; Nitric acid, sulfuric acid or a salt thereof; Polyhydric alcohol type surfactants; And residual water, and is a composition for etching both the copper-based metal film and the laminated film of the copper-based metal film and the metal oxide film.

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 layer of the copper-based metal film described above, or a multi-layered film may include a copper-molybdenum film or a copper-molybdenum alloy film or a copper-titanium film, but the present invention is not limited thereto. Wherein the copper-molybdenum film includes a molybdenum layer and the copper-based metal film formed on the molybdenum layer, and the copper-molybdenum alloy film includes the molybdenum alloy layer and the copper-based metal film formed on the molybdenum alloy layer it means. The copper-titanium film includes a titanium layer and the copper-based metal film formed on the titanium layer. 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). More specific examples of the metal oxide include InGaZnO, GaZnO, InSnO, InZnO and the like, but are not limited thereto.

<Hydrogen Peroxide>

The hydrogen peroxide contained in the etchant composition of the present invention is the main component for etching the copper-based metal film. Hydrogen peroxide is included in an amount of 15 to 25% by weight, preferably 18 to 23% by weight, based on the total weight of the composition. When the content is less than 15% by weight, the copper-based metal film is not etched or the etching rate is extremely slow. When the content is more than 25% by weight, the etching rate is entirely accelerated, so that it is difficult to control the etching degree and the process control becomes difficult.

<Fluorine-Containing Compound>

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 copper-based metal 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 0.1 to 0.4% 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 ), Sodium bifluoride (NaF.HF), and potassium bifluoride (KF.HF).

< Azole  Compound &gt;

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 1.0% by weight, preferably 0.3 to 0.8% by weight based on the total weight of the composition. If the content is less than 0.1% by weight, CD loss may occur too much, and if it exceeds 5% by weight, etching rate of the copper-based metal film may become too slow, so that etching residues may occur and the processing time may become 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, benzotriazole, tolyltriazole, 1,2,4-triazole, etc. 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-amino-1-phenyltetrazole, 5-amino-1 (1-naphthyl) tetrazole, 1,5-diaminotetrazole, and the like. Aminotetrazole can be preferably used.

&Lt; Water-soluble compound having nitrogen atom and carboxyl group in one molecule >

The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the etching solution composition of the present invention prevents the self-decomposition reaction of the hydrogen peroxide solution that may occur in the storage of the etching solution composition and changes the etching property when a large number of substrates are etched &Lt; / RTI &gt; In general, the etching solution composition using hydrogen peroxide water has a risk that the storage of the hydrogen peroxide is self-decomposed during storage and the container can explode because the storage period is not long. However, when a water-soluble compound having a nitrogen atom and a carboxyl group is contained in one molecule, the decomposition rate of the hydrogen peroxide solution is reduced to about 10 times, which is advantageous for securing the storage period and stability. Particularly in the case of the copper layer, if a large amount of copper ions remain in the etchant composition, a passivation film may be formed and then the resultant may not be further etched after being oxidized. However, .

The content of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule may be 0.5 to 5% by weight, preferably 1 to 3% by weight based on the total weight of the composition. When the content is less than 0.5 wt%, a passivation film is formed after etching a large number of substrates (about 500 sheets), making it difficult to obtain a sufficient process margin. If the content is more than 5% by weight, the etching rate of the copper-based metal film may be slowed to cause an etching residue.

Examples of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, Nitrilotriacetic acid, ethylenediamine tetraacetic acid, sarcosine and the like may be used alone or in admixture of two or more kinds. Preferably, iminodiacetic acid may be used. have.

< Glycolic acid >

The glycolic acid contained in the etchant composition of the present invention controls the etching rate of the copper-based metal film by increasing the activity of the hydrogen peroxide and the fluorine-containing compound by adjusting the pH.

The glycolic acid is contained in an amount of 0.5 to 3.0% by weight, preferably 1.0 to 2.0% by weight, based on the total amount of the composition. When the content is less than 0.5% by weight, the etching rate of the copper-based metal film is lowered. When the content is more than 3.0% by weight, excessive etching failure occurs due to too high etching rate of the copper-based metal film.

< Glycolic acid  Organic acid>

The organic acid other than the glycolic acid contained in the etchant composition of the present invention controls the etching rate of the copper-based metal film and the metal oxide film by increasing the activity of the hydrogen peroxide and the fluorine-containing compound by controlling the pH of the etching solution.

The organic acid excluding the glycolic acid is contained in an amount of 0.5 to 3.0% by weight, preferably 1.0 to 2.0% by weight based on the total amount of the composition. If the content is less than 0.5% by weight, the etching rate of the metal film or metal oxide film (for example, molybdenum, molybdenum alloy film, indium oxide film or indium oxide alloy film) Excessive erosion failure due to too high etch rate of the film occurs.

The organic acid other than the glycolic acid is an organic acid which does not overlap with the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule described above. For example, an organic acid not containing a nitrogen atom. As a more specific example, organic acids include butanoic acid, citric acid, formic acid, gluconic acid, malonic acid, pentanoic acid, lactic acid, acid, and oxalic acid, and malonic acid may be preferably used.

&Lt; Nitric acid, sulfuric acid or its salt &

The nitric acid, sulfuric acid, or a salt thereof contained in the etchant composition of the present invention maintains the amount of etching change during the process of adjusting the pH.

Nitric acid, sulfuric acid or a salt thereof is contained in an amount of 0.1 to 2.0% by weight, preferably 0.5 to 1.0% by weight, based on the total amount of the composition. If the content is less than 0.1 wt%, the etching change amount can not be maintained in repeating the etching process of the copper-based metal film. If the content is more than 2.0 wt%, the morphology of the copper-based metal film is deteriorated.

In the present invention, among inorganic acids or salts thereof, nitric acid or sulfuric acid or a salt thereof is included. Nitric acid or sulfuric acid or a salt thereof may exhibit the above-described function desired in the present invention. Hydrochloric acid, which is another inorganic acid, damages the copper-based metal film and the metal oxide film, and the phosphoric acid may lower the etching rate of the metal film or metal oxide film (for example, molybdenum film, molybdenum alloy film, indium oxide film, or indium oxide alloy film) .

More specific examples of the salt of nitric acid or sulfuric acid include at least one kind selected from the group consisting of potassium salt, calcium salt, sodium salt and ammonium salt, but is not limited thereto.

< Polyhydric alcohol type  Surfactants>

The polyhydric alcohol type surfactant contained in the etchant composition of the present invention lowers the surface tension and increases the uniformity of the etching. In addition, the etching of the copper film surrounds the copper ions dissolved in the etching solution, thereby suppressing the activity of copper ions and inhibiting the decomposition reaction of hydrogen peroxide. Thus, lowering the activity of the copper ion allows the process to proceed stably while using the etchant.

The content of the polyhydric alcohol type surfactant is 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the total weight of the composition. If the content is less than 0.001% by weight, etching uniformity may be deteriorated and decomposition of hydrogen peroxide may be accelerated. When the content is more than 5.0% by weight, bubbles may be generated.

Examples of the polyhydric alcohol type surfactant that can be used include glycerol, triethylene glycol, and polyethylene glycol, which may be used alone or in combination of two or more. Triethylene glycol may be used.

<Water>

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.

<Additives>

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 etchant 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 a material of the gate wiring, a molybdenum film, a molybdenum alloy film, the copper-based metal film described above, or a lamination film of the copper-based metal film and the metal oxide film described above may be used. In particular, a lamination film of a copper-based metal film and a metal oxide film is preferable.

The gate wiring can be formed by etching the molybdenum film, the molybdenum alloy film, the copper-based metal film, or the laminated film of the copper-based metal film and the metal oxide film in a pattern required for 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.

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, a copper-based metal film or a lamination film of the copper-based metal film and the metal oxide film described above may be used, and a copper-based metal film is particularly preferable.

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

In the present invention, the etchant for forming the gate wiring and the source and drain wirings may be an etchant of the same composition.

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

Hydrogen peroxide A B C D E F G Deionized water Kinds content Kinds content Kinds content Kinds content Kinds content Kinds content Example 1 15 A-1 0.2 B-1 0.3 C-1 1.0 1.0 E-1 One F-1 0.5 G-1 0.5 Balance Example 2 18 A-1 0.2 B-1 0.5 C-2 1.0 1.0 E-1 One F-2 0.5 G-1 1.0 Balance Example 3 20 A-1 0.2 B-2 0.5 C-2 1.5 1.5 E-2 2 F-1 0.5 G-2 1.0 Balance Example 4 23 A-2 0.2 B-2 0.8 C-1 2.0 1.5 E-2 2 F-2 1.0 G-1 1.5 Balance Example 5 25 A-2 0.3 B-1 1.0 C-1 2.0 2.0 E-2 2 F-2 1.0 G-2 2.0 Balance Comparative Example 1 18 A-1 0.2 B-1 0.5 C-1 1.0 1.0 E-1 - F-3 1.0 G-1 1.0 Balance Comparative Example 2 18 A-1 0.2 B-1 0.5 C-1 1.0 1.0 E-1 - F-1 0.5 G-1 1.0 Balance Comparative Example 3 20 A-1 1.5 B-2 0.5 C-2 1.5 1.5 E-2 2 F-1 0.5 G-2 1.0 Balance Comparative Example 4 20 A-1 0.2 B-2 1.5 C-2 1.5 1.5 E-2 2 F-1 0.5 G-2 1.0 Balance Comparative Example 5 20 A-1 0.2 B-2 0.5 C-2 5.5 1.5 E-2 2 F-1 0.5 G-2 1.0 Balance Comparative Example 6 20 A-1 0.2 B-2 0.5 C-2 1.5 4.5 E-2 2 F-1 0.5 G-2 1.0 Balance Comparative Example 7 20 A-1 0.2 B-2 0.5 C-2 1.5 1.5 E-2 4 F-1 0.5 G-2 1.0 Balance Comparative Example 8 20 A-1 0.2 B-2 0.5 C-2 1.5 1.5 E-2 2 F-1 3.5 G-2 1.0 Balance Comparative Example 9 20 A-1 0.2 B-2 0.5 C-2 1.5 1.5 E-2 2 F-1 0.5 G-2 6.0 Balance A: Fluorine-containing compound
A-1: NH ₄ F
A-2: KFHF

B: azole compound
B-1: Aminotetrazole
B-2: 1,2,4-triazole

C: a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule
C-1: iminodiacetic acid
C-2: Ethylenediamine tetraacetic acid

D: glycolic acid

E: organic acid excluding glycolic acid
E-1: Malonic acid
E-2: Lactic acid

F: nitric acid, sulfuric acid or a salt thereof
F-1: Ammonium sulfate
F-2: Ammonium nitrate
F-3: Ammonium phosphate monobasic

G: polyhydric alcohol type surfactant
G-1: Triethylene glycol
G-2: Polyethylene glycol

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. The copper-based metal film and the metal oxide film were subjected to an etching process using the compositions of Examples 1 to 5 and Comparative Examples 1 to 9, 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 film 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 batch Etching

A Mo-Ti alloy 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. The copper-based metal film and Mo-Ti were subjected to an etching process using the compositions of Examples 1 to 5 and Comparative Examples 1 to 9, 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 / Mo-Ti film 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

Pattern Out: Over-etching

< 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

Pattern Out: Over-etching

< Mo - Ti membrane tail  Evaluation criteria>

?: Less than 0.10 占 퐉

?: 0.10 占 퐉 or more to less than 0.20 占 퐉

Х: 0.20 ㎛ or more

Unetch: not etched

Pattern Out: Over-etching

< ITO membrane tail  Evaluation criteria>

?: Less than 0.45 占 퐉

?: 0.45 占 퐉 or more to less than 0.60 占 퐉

Х: 0.60 ㎛ or more

Unetch: not etched

Pattern Out: Over-etching

Etching profile Etching straightness tail Cu / Mo-Ti Cu / ITO Cu / Mo-Ti Cu / ITO Cu / Mo-Ti Cu / ITO Example 1 ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ ○ Comparative Example 1 ○ Unetch ○ Unetch ○ Unetch Comparative Example 2 ○ △ ○ △ ○ X Comparative Example 3 X X X X ○ ○ Comparative Example 4 Unetch Unetch Unetch Unetch Unetch Unetch Comparative Example 5 ○ Unetch ○ Unetch ○ Unetch Comparative Example 6 Pattern out Pattern out Pattern out Pattern out Pattern out Pattern out Comparative Example 7 Pattern out Pattern out Pattern out Pattern out Pattern out Pattern out Comparative Example 8 Pattern out Pattern out Pattern out Pattern out Pattern out Pattern out Comparative Example 9 Unetch Unetch Unetch Unetch Unetch Unetch

As shown in Table 2, the etching solution compositions of Examples 1 to 5 all exhibited good etching properties. Therefore, it can be seen that the etching solution composition of the present invention is very suitable for etching the copper-based metal film, and is also very bonded to the batch etching thereof.

However, in Comparative Example 1 containing phosphate, unetching phenomenon occurred due to phosphate functioning as an inhibitor in ITO etching. In addition, in Comparative Example 2 in which no organic acid except glycolic acid was added, it was confirmed that the ITO tail was increased, and the ITO etching profile and the linearity were lowered.

Further, in the case of the etching solution of Comparative Example 3 in which the fluorine-containing compound was added in an excessive amount, an undercut (erosion between the Cu and the Cu lower film) occurred. Also, in Comparative Example 4 in which an azole compound was added in excess, a Cu unetching phenomenon occurred. In Comparative Example 5 in which an excessive amount of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule was present, ITO unetching phenomenon occurred. In Comparative Example 6 in which glycolic acid was excessively contained and Comparative Example 7 in which an organic acid was excessively contained, Pattern Out A phenomenon has occurred. In Comparative Example 8 in which nitric acid, sulfuric acid, or a salt thereof was contained in an excessive amount, pattern out phenomenon occurred, and in Comparative Example 9 in which an excess amount of surfactant was contained, unetching phenomenon occurred.

Referring to FIGS. 1 and 2, when the etchant composition of Example 2 is etched, it is confirmed that the taper profile, the etching straightness, and the tails of Mo-Ti are excellent.

However, referring to FIG. 3 and FIG. 4, it can be seen that the ITO is unetched when the etchant composition of Comparative Example 1 is etched.

Referring to FIGS. 5 and 6, it can be seen that when the etching composition of Comparative Example 2 is etched, the ITO tail becomes long.

Claims (17)

A water-soluble compound having a nitrogen atom and a carboxyl group in one molecule in an amount of 0.5 to 5 wt%, a glycolic acid in an amount of 0.5 to 3.0 wt%, a glycol A copper-based metal film and a copper-based metal film containing 0.5 to 3.0 wt% of organic acid excluding acid, 0.1 to 2.0 wt% of nitric acid, sulfuric acid or its salt, 0.001 to 5.0 wt% of polyhydric alcohol type surfactant, Oxide film.
The method according to claim 1, 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 F · A copper-based metal film which is at least one selected from the group consisting of HF, sodium bifluoride (NaF.HF) and potassium bifluoride (KF.HF), a copper-based metal film and a metal- Film etchant 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- A copper-based metal film and a metal oxide film, wherein the copper-based metal film and the metal-oxide film are at least one selected from the group consisting of a fluorine-based compound and a pyrrole-based compound.
The water-soluble compound according to claim 1, wherein the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule is selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, A copper-based metal film and at least one copper-based metal film selected from the group consisting of nitrilotriacetic acid, ethylenediamine tetraacetic acid, and sarcosine, and a copper-based metal film and a metal oxide film.
The organic acid according to claim 1, wherein the organic acid excluding the glycolic acid is at least one selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, malonic acid, pentanoic acid, lactic acid, A laminated film etchant composition comprising a metal film and a metal oxide film.
The method according to claim 1, wherein the salt of nitric acid or sulfuric acid is at least one selected from the group consisting of potassium salt, calcium salt, sodium salt and ammonium salt of nitric acid or sulfuric acid, and a copper- Etchant composition.
The polyvalent alcohol surfactant according to claim 1, wherein the polyvalent alcohol surfactant is at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol, a copper-based metal film and a copper- A laminated film etchant composition for a metal oxide film.
[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 a copper-based metal film and a metal oxide film, wherein the copper-based metal film and the metal-based metal film are formed of an alloy of at least one metal selected from the group consisting of copper,
The copper-based metal film according to claim 8, 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 A copper-based metal film comprising a copper-molybdenum alloy film or a copper-titanium film including the copper-based metal film formed on a titanium layer, and a laminated film etchant composition of a copper-based metal film and a metal oxide 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, ), A copper-based metal film, a copper-based metal film, and a metal oxide 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) A method of forming a wiring, comprising: 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 10.
12. The method of claim 11, wherein the metal oxide film is formed of a material 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.
12. The method of claim 11, 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 13, 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:
The step a) includes forming a metal film on the substrate, and then etching the metal film with the etching solution composition of any one of claims 1 to 10 to form a gate wiring,
The step d) includes forming a source and a drain wiring by etching the metal film with the etching solution composition according to any one of claims 1 to 10 after forming a metal film on the semiconductor layer,
The metal film in the steps a) and d) is a copper-based metal film or a laminated film of a copper-based metal film and a metal oxide film,
Wherein the etchant of steps a) and d) is the same etchant.
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 a), a copper-based metal film and a metal oxide film are laminated on the substrate, and then the copper-based metal film and the metal oxide film are etched with the etchant composition of any one of claims 1 to 10, ; And
The step d) includes forming a copper-based metal film on the semiconductor layer, and etching the copper-based metal film with the etching solution composition according to any one of claims 1 to 10 to form a source and a drain wiring,
Wherein the etchant of steps a) and d) is the same etchant.
The method according to claim 16, wherein the copper-based metal film in step d) is a copper-molybdenum film or a copper-molybdenum alloy film.

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