KR20160109569A - Etchant composition and manufacturing method of an array for liquid crystal display - Google Patents

Abstract

The present invention relates to an etching solution composition and a method for producing an array substrate for liquid crystal display devices. According to the present invention, the etching solution composition contains precious metal compounds and thus creates catalytic effects. Thus, it is possible to integrally etch, via a wet-type etching process along with an upper metal wire, both impurity-included amorphous silicone layers and amorphous silicone which were once etched via a conventional dry-type method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an etchant composition and an array substrate for a liquid crystal display,

The present invention relates to an etching liquid composition and a method of manufacturing an array substrate for a liquid crystal display.

The process of forming a metal wiring on a substrate in a semiconductor device is generally composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process , A cleaning process before and after the individual unit process, and the like. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.

In such a semiconductor device, resistance of metal wiring has recently become a major concern. This is because the resistance is a key factor that causes the RC signal delay, especially in the case of TFT-LCD (thin film transistor-liquid crystal display), because the increase in panel size and realization of high resolution are the key to technology development. Therefore, in order to realize reduction of the RC signal delay which is indispensably required for enlarging the TFT-LCD, it is essential to develop a low resistance material. Thus, the chromium which was mainly used conventionally (Cr, specific resistance: 12.7 × 10 ^-8 Ωm), molybdenum (Mo, specific resistance: 5 × 10 ^-8 Ωm), aluminum (Al, specific resistance: 2.65 × 10 ^-8 Ωm) and their Is difficult to use as a gate and data wiring used in a large-sized TFT LCD.

Under such background, there is a high interest in a copper-based metal film such as a copper film and a copper molybdenum film and an etchant composition thereof as a new low-resistance metal film, and studies for this have been actively conducted. For example, Korean Patent Laid-Open Publication No. 2010-0090538 discloses a hydrogen peroxide, an organic acid, a phosphate compound, a water-soluble cyclic amine compound, a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, , A polyhydric alcohol type surfactant, and water. However, in the case of the etchant, the amorphous silicon layer and the amorphous silicon layer including impurities are not etched.

Korea Patent Publication No. 2010-0090538

The present invention provides an etchant composition capable of performing batch etching of an amorphous silicon layer and an impurity-containing amorphous silicon layer that have been etched through a conventional dry method, together with an upper metal interconnection by a wet etching process.

The present invention relates to a water-soluble compound having 10 to 35 wt% of hydrogen peroxide, 0.5 to 5 wt% of organic acid, 0.1 to 5 wt% of phosphoric acid or phosphate, 0.1 to 5 wt% of a water-soluble cyclic amine compound, Based metal film and a silicon layer comprising 0.1 to 5% by weight of a fluorine compound, 0.01 to 0.9% by weight of a fluorine compound, 0.01 to 2% by weight of a noble metal compound, and water balance.

In one embodiment of the present invention, the organic acid is selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, and pentanoic acid.

In another embodiment, the water-soluble cyclic amine compound is an aminotetrazole, an imidazole, an indole, a purine, a pyrazole, a pyridine, a pyrimidine, Pyrrole, pyrrolidine, quinolone, and pyrroline. In the present invention, it is preferable that the at least one compound is at least one selected from the group consisting of pyrrolidine, pyrrolidine, quinolone, and pyrroline.

In another embodiment, the water-soluble compound having an amino group and a carboxylic acid group in one molecule is alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, , Nitrilotriacetic acid, and sarcosine. In the present invention,

In another embodiment, the fluorine compound is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, and the like.

In another embodiment, the noble metal compound may be at least one selected from the group consisting of copper, silver, and gold.

In another embodiment, the copper-based metal film is a single film of copper or a copper alloy; Or a copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer, a copper molybdenum alloy film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, a titanium layer and a copper layer formed on the titanium layer Layer or a copper-titanium alloy film including a titanium alloy layer and a copper layer formed on the titanium alloy layer.

The present invention also provides a method of manufacturing a semiconductor device, comprising the steps of: 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 source and drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

The step a) includes forming a copper-based metal film on the substrate and etching the copper-based metal film with the etchant composition to form a gate wiring, wherein the step d) includes forming a copper- Etching the substrate with an etchant composition to form source and drain electrodes,

Wherein the etchant composition comprises 10 to 35 wt% of hydrogen peroxide, 0.5 to 5 wt% of organic acid, 0.1 to 5 wt% of phosphoric acid or phosphate, 0.1 to 5 wt% of a water-soluble cyclic amine compound, And 0.1 to 5% by weight of a water-soluble compound having an acid group, 0.01 to 0.9% by weight of a fluorine compound, 0.01 to 2% by weight of a noble metal compound, and water balance. .

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

In another embodiment, the copper-based metal film is a single film of copper or a copper alloy; Or a copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer, a copper molybdenum alloy film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, a titanium layer and a copper layer formed on the titanium layer Layer or a copper-titanium alloy film including a titanium alloy layer and a copper layer formed on the titanium alloy layer.

The etchant composition of the present invention is characterized in that the catalytic effect is caused by the inclusion of a noble metal compound. Accordingly, the amorphous silicon layer and the amorphous silicon layer, which have been etched through the conventional dry process, are subjected to a wet etching process, There is an advantage to be able to do.

The present invention relates to an etching liquid composition and a method of manufacturing an array substrate for a liquid crystal display. The etchant composition of the present invention is characterized in that the catalytic effect is caused by the inclusion of a noble metal compound. Accordingly, the amorphous silicon layer and the amorphous silicon layer, which have been etched through the conventional dry process, are subjected to a wet etching process, There is an advantage to be able to do.

Hereinafter, the present invention will be described in detail.

The present invention relates to a water-soluble compound having 10 to 35 wt% of hydrogen peroxide, 0.5 to 5 wt% of organic acid, 0.1 to 5 wt% of phosphoric acid or phosphate, 0.1 to 5 wt% of a water-soluble cyclic amine compound, Based metal film and a silicon layer comprising 0.1 to 5% by weight of a fluorine compound, 0.01 to 0.9% by weight of a fluorine compound, 0.01 to 2% by weight of a noble metal compound, and water balance.

A copper / molybdenum alloy film or a copper / titanium alloy film composed of wirings of LCD, OLED thin film transistors in the etchant composition of the present invention is formed as wirings serving as an electric circuit. In addition, in the case of forming an active layer made of a silicon system which has been formed through a conventional dry etching process, the wet etching can be performed through the etch solution and the catalytic action of the noble metal, thereby reducing the processing cost and time.

The copper-based metal film may be a single film of copper or a copper alloy; Or a copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer, a copper molybdenum alloy film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, a titanium layer and a copper layer formed on the titanium layer Layer or a copper-titanium alloy film including a titanium alloy layer and a copper layer formed on the titanium alloy layer.

Specifically, the molybdenum alloy layer may be formed of a single layer of molybdenum or a single layer of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), aluminum (Al), palladium (Pd) In and molybdenum may be used as the titanium alloy layer. The titanium alloy layer may be formed of a single layer of titanium or a metal such as molybdenum (Mo), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) , Aluminum (Al), palladium (Pd), and indium (In), and titanium.

The silicon system may be one of silicon or amorphous silicon including impurities, and the amorphous silicon containing the impurities may be formed of amorphous silicon containing boron (B) and phosphorus (P) as impurities.

The structure of the copper / molybdenum alloy layer or the copper / titanium alloy layer may be a triple-layer structure in which a molybdenum alloy layer or a titanium alloy layer is laminated on both the upper and lower layers as well as the upper and lower layers of the copper film.

On the other hand, a glass substrate for a TFT-LCD, a TFT-OLED and a touch sensor panel (TSP) is used as the substrate.

The etchant composition according to the present invention can collectively etch the gate wiring for the gate electrode and the data electrode data line of the display device made of the copper layer and the molybdenum alloy or the copper layer and the titanium alloy layer.

The hydrogen peroxide in the etchant composition will comprise from 10 to 35% by weight based on the total weight of the etchant composition. If the content of hydrogen peroxide is less than 10% by weight, the etching rate is very slow, the process is difficult to proceed, a sufficient amount of etching is not performed, and etching of the copper, molybdenum alloy film, titanium alloy film and silicon- There may be a defect that remains of the residue, which is a phenomenon in which a part is not etched. On the other hand, if the content exceeds 35 wt%, it is difficult to control the etching rate, and there is a risk of accelerating the reaction of the fruit body itself due to the radical reaction of the metal such as copper during the etching and explosion.

The organic acid in the etchant composition contains 0.5 to 5% by weight based on the total weight of the etchant composition. The organic acid is a main component which etches the copper layer and the molybdenum alloy layer or the copper layer and the titanium layer together with the hydrogen peroxide. It is preferable to use the one having the purity for the semiconductor process together with the hydrogen peroxide so that the metal impurities are below the ppb level. The organic acid also controls the copper etching rate and the etching rate of the molybdenum alloy or titanium alloy by adjusting the pH. The appropriate pH for the addition of organic acid is about 0.5 to 4.5.

The organic acid may be selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, And may be any one selected from pentanoic acid.

The phosphoric acid or phosphate in the etchant composition may comprise from 0.1 to 5% by weight based on the total weight of the etchant composition. Phosphoric acid or phosphate is a component that improves the taper profile of the wiring (angle formed perpendicular to the lower layer) and reduces the electric effect (galvanic effect) between the molybdenum alloy or titanium alloy and copper to form a molybdenum alloy layer or a titanium alloy It prevents the undercut phenomenon that the layer penetrates deeply into the bottom of the copper layer. If phosphoric acid or phosphate is not contained or less than 0.1 wt% is contained, the molybdenum alloy layer or the titanium alloy layer is excessively etched down to the upper copper layer, and if severe, the pattern may be removed from the substrate. If the phosphoric acid or the phosphate is contained in an amount of more than 5 wt%, the etching rate of the molybdenum alloy layer or the titanium alloy layer may be reduced and the electrical shorting may be caused by the tail phenomenon.

The phosphoric acid salt may be of various types, and it is preferable to use phosphoric acid in which hydrogen is selected from one, two or three substituted salts of alkali metal or alkaline earth metal. Examples of the phosphate include sodium dihydrogen phosphate, potassium dihydrogen phosphate, and the like.

The water-soluble cyclic amine compound in the etchant composition contains 0.1 to 5% by weight based on the total weight of the etchant composition. The water-soluble cyclic amine compound controls the etch rate of the copper molybdenum alloy and reduces the CD loss of the pattern, thereby enhancing the process margin. When the water-soluble cyclic amine compound is not contained or is contained in an amount of less than 0.1% by weight, it is difficult to control the etching rate and the width of a desired pattern can not be obtained. Thus, there is a high probability of defect, It is different. In addition, even if the amount exceeding 5% by weight is included, the etching rate is considerably slowed, making it impossible to apply to the process.

Examples of the water-soluble cyclic amine compound include various amines such as aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, it is preferably one of pyrimidine, pyrrole, pyrrolidine, quinolone and pyrroline.

The water-soluble compound having an amino group and a carboxylic acid group in one molecule of the etching solution composition contains 0.1 to 5% by weight based on the total weight of the etching solution composition. A water-soluble compound having an amino group and a carboxylic acid group in one molecule prevents the self-decomposition reaction of hydrogen peroxide which may occur during the storage of the etching solution, and when a large number of substrates are etched, the etching property . When a water-soluble compound having an amino group and a carboxylic acid group is contained in one molecule, the decomposition rate of the hydrogen peroxide water is reduced to about 10 times, which is advantageous for securing the storage period and stability. In addition, by inactivating copper, molybdenum alloy, and titanium alloy ions, which are inevitably generated during copper, molybdenum alloy film and titanium alloy film etching, by chelation reaction, it is possible to prevent additional reactions that may be caused by ions, Even when the substrate is etched, the etching characteristics are not changed as the metal ion concentration increases. Particularly, in the case of copper layer, when a large amount of copper ions are left in the etching solution, a passivation film is formed and then it is not oxidized after it is oxidized. However, when this compound is added, the phenomenon can be prevented . If such a water-soluble compound having an amino group and a carboxylic acid group in a molecule is contained in an amount exceeding 5% by weight, it affects the etching rate, which inhibits the etching composition from forming a metal wiring of a desired shape, which is a cause of defects.

Examples of water-soluble compounds having an amino group and a carboxylic acid group in one molecule include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid, acid, and sarcosine.

The fluorine compound in the etchant composition may include 0.1 to 0.9% by weight based on the total weight of the etchant composition. The fluorine compound serves to remove residues that are inevitably generated in the solution which simultaneously etches the copper layer and the molybdenum alloy layer. The silicon layer is etched through the dissociation process by fluorine ion Plays a very important role. Further, the fluorine compound is used as a stock agent through a dissociation reaction of an active layer composed of a silicon system oxidized by a peroxide.

Copper is generally known to be the most etched at low pH (2 to 4), while molybdenum alloys are found to be most smoothly etched at slightly acidic or nearly neutral pH (5 to 7). That is, in order to simultaneously etch the copper layer and the molybdenum alloy layer, one must inevitably focus on one of the copper layer or the molybdenum alloy layer. At this time, the thicker layer is focused on. In general, since the thickness of the copper layer becomes much thicker, the pH becomes low. An etching solution having a pH of about 2 to 4 can etch the molybdenum alloy layer to some extent, even though the etching rate is slow, while the copper layer is smoothly etched. However, due to the characteristics of the molybdenum alloy layer, it is inevitably generated as small particle type residues. If residues are formed and remain on the glass substrate or the lower film, electrical shorting occurs or the luminance is lowered. It is the fluorine compound that must be added to the etching solution essentially to remove the residue. The fluorine compound has the disadvantage of etching the glass substrate, the silicon nitride and the silicon oxide layer, but the etching can be prevented if the concentration is too small.

In the etchant composition of the present invention, the fluorine compound is added in an amount of 0.01 to 0.9% by weight, and the porous or impurity-containing silicon used as the active layer can be etched, while the glass substrate, The passivation layer such as the silicon oxide layer is in a range where no etching occurs. Even if the passivation layer is added in such a small amount, the residue of the molybdenum alloy layer can be sufficiently removed.

As the fluorine compound, various types can be used, and examples thereof include ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, Potassium bifluoride, and the like.

The noble metal compound in the etchant composition is contained in an amount of 0.1 to 2% by weight, and serves as a catalyst for lowering the activation energy so that the oxidation reaction easily occurs on the silicon surface. The noble metal compound and the silicon layer surface-oxidized by the water are etched by the fluorine compound.

If the content of the noble metal compound is less than 0.1% by weight, the silicon-based active layer can not be etched because it can not serve as a metal catalyst. If the noble metal compound is contained in an amount exceeding 2% by weight, , The etching solution may lose the original role of the etching solution due to the reduction of the etching rate, and if the rapid decomposition occurs, it may lead to an explosion.

The noble metal compound may be one or more selected from the group consisting of copper, silver and gold, and the noble metal compound may include a copper compound, a silver compound and the like.

The copper compound may be one selected from the group consisting of copper nitrate, copper sulfate, copper phosphate, copper chloride and copper acetate. The silver compound is preferably silver nitrate, silver sulfate, and phosphoric acid.

Water is not particularly limited, but deionized water is preferred. More preferably, deionized water having a resistivity value of water of 18 M / cm or more (that is, the degree of removal of ions in water) is used.

It is needless to say that other conventional additives may be added as necessary. Examples of other additives that may be added include, but are not limited to, surfactants, metal ion sequestrants, and corrosion inhibitors.

Here, the surfactant may be added to lower the surface tension to increase the uniformity of the etching, and as such a surfactant, a surfactant which is resistant to the etching solution and has compatibility with the surfactant is preferable. For example, any anionic, cationic, amphoteric or nonionic surfactant. Further, preferably, a fluorine-based surfactant may be added as a surfactant.

The present invention also provides a method of manufacturing a semiconductor device, comprising the steps of: 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 source and drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

The step a) includes forming a copper-based metal film on the substrate and etching the copper-based metal film with the etchant composition to form a gate wiring, wherein the step d) includes forming a copper- Etching the substrate with an etchant composition to form source and drain electrodes,

Wherein the etchant composition comprises 10 to 35 wt% of hydrogen peroxide, 0.5 to 5 wt% of organic acid, 0.1 to 5 wt% of phosphoric acid or phosphate, 0.1 to 5 wt% of a water-soluble cyclic amine compound, And 0.1 to 5% by weight of a water-soluble compound having an acid group, 0.01 to 0.9% by weight of a fluorine compound, 0.01 to 2% by weight of a noble metal compound, and water balance. .

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

Example  1 to 23 and Comparative Example  1 to 14. Etchant  Preparation of composition

The etchant composition was prepared with the compositions and contents (% by weight) shown in Tables 1 and 2 below.

division (A) (B) (C) (D) (E) (F) (G) (H) (b1) (b2) (b3) (c1) (c2) (d1) (d2) (d3) (e1) (e2) (f1) (f2) (g1) (g2) Example 1 25 One One One 1.5 0.5 One Balance Example 2 25 One One One 1.5 0.5 One Balance Example 3 25 One One One 1.5 0.5 One Balance Example 4 25 One One One 1.5 0.5 One Balance Example 5 25 One One One 1.5 0.5 One Balance Example 6 25 0.5 One One 1.5 0.5 One Balance Example 7 25 4 One One 1.5 0.5 One Balance Example 8 25 One One One 1.5 0.5 One Balance Example 9 25 One 0.3 One 1.5 0.5 One Balance Example 10 25 One 4.5 One 1.5 0.5 One Balance Example 11 25 One One One 1.5 0.5 One Balance Example 12 25 One One One 1.5 0.5 One Balance Example 13 25 One One 0.15 1.5 0.5 One Balance Example 14 25 One One 4.5 1.5 0.5 One Balance Example 15 25 One One One 1.5 0.5 One Balance Example 16 25 One One One 0.2 0.5 One Balance Example 17 25 One One One 4 0.5 One Balance Example 18 25 One One One 1.5 0.5 One Balance Example 19 25 One One One 1.5 0.1 One Balance Example 20 25 One One One 1.5 0.9 One Balance Example 21 25 One One One 1.5 0.5 One Balance Example 22 25 One One One 1.5 0.5 0.1 Balance Example 23 25 One One One 1.5 0.5 1.5 Balance (A): hydrogen peroxide
(B): Organic acid
(b1): glycolic acid
(b2): Citric acid
(b3): malonic acid
(C): phosphoric acid or phosphate
(c1): sodium dihydrogenphosphate
(c2): potassium dihydrogen phosphate
(D): Water-soluble cyclic amine compound
(d1): Aminotetrazole
(d2): imidazole
(d3): Pyridine
(E): a water-soluble compound having an amino group and a carboxylic acid group in one molecule
(e1): glycine
(e2): iminodiacetic acid
(F): fluorine compound
(f1): Ammonium fluoride
(f2): Ammonium fluoride
(G): noble metal compound
(g1): copper sulfate
(g2): silver nitrate
(H): Water

division (A) (B) (C) (D) (E) (F) (G) (H) (b1) (b2) (b3) (c1) (c2) (d1) (d2) (d3) (e1) (e2) (f1) (f2) (g1) (g2) Comparative Example 1 9 One One One 1.5 0.5 One Balance Comparative Example 2 36 One One One 1.5 0.5 One Balance Comparative Example 3 25 0.4 One One 1.5 0.5 One Balance Comparative Example 4 25 6 One One 1.5 0.5 One Balance Comparative Example 5 25 One One 1.5 0.5 One Balance Comparative Example 6 25 One 5.5 One 1.5 0.5 One Balance Comparative Example 7 25 One One 1.5 0.5 One Balance Comparative Example 8 25 One One 5.5 1.5 0.5 One Balance Comparative Example 9 25 One One One 0.5 One Balance Comparative Example 10 25 One One One 6 0.5 One Balance Comparative Example 11 25 One One One 1.5 One Balance Comparative Example 12 25 One One One 1.5 One One Balance Comparative Example 13 25 One One One 1.5 0.5 Balance Comparative Example 14 25 One One One 1.5 0.5 2.5 Balance (A): hydrogen peroxide
(B): Organic acid
(b1): glycolic acid
(b2): Citric acid
(b3): malonic acid
(C): phosphoric acid or phosphate
(c1): sodium dihydrogenphosphate
(c2): potassium dihydrogen phosphate
(D): Water-soluble cyclic amine compound
(d1): Aminotetrazole
(d2): imidazole
(d3): Pyridine
(E): a water-soluble compound having an amino group and a carboxylic acid group in one molecule
(e1): glycine
(e2): iminodiacetic acid
(F): fluorine compound
(f1): Ammonium fluoride
(f2): Ammonium fluoride
(G): noble metal compound
(g1): copper sulfate
(g2): silver nitrate
(H): Water

Experimental Example  One. Etch characteristics  evaluation

Copper (Cu), a molybdenum titanium alloy film (MoTi), a titanium film (Ti), and a hydrogenated amorphous silicon layer (a-Si: H) were deposited on a glass substrate (100 mm × 100 mm).

The four samples were etched using the etchant compositions of Examples 1 to 23 and Comparative Examples 1 to 14, respectively. The temperature of the etchant composition was set at 30 ° C. during the etching process. When the temperature reached 30 ± 0.1 ° C., the etch process of the sample was performed at 20 ° C., 40, 60, 80, 100 seconds. After cleaning and drying, the etched thickness with time was evaluated using an electron microscope (SEM; model name: SU-8010, manufactured by Hitachi), and evaluated according to the evaluation criteria of Table 3. The results are shown in Table 4 and Table 5

Experimental Example  2. pH evaluation

Each of the etching composition compositions of Examples 1 to 23 and Comparative Examples 1 to 14 was measured using a pH meter (manufactured by Thermoscientific, model: Orion 3 star) and evaluated according to the evaluation criteria shown in Table 3, 4 and Table 5, respectively.

Experimental Example  3. Overeating angle  evaluation

A hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a molybdenum titanium alloy film (MoTi), and a hydrogenated amorphous silicon layer (Cu) were sequentially deposited on the substrate. As another sample, a hydrogenated amorphous silicon layer (a-Si: H), a hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a titanium film (Ti) , And copper (Cu) were sequentially deposited. Thereafter, a photoresist (PR) having a predetermined pattern was formed through a photolithography process.

The two samples were subjected to an etching process using each of the etching liquid compositions of Examples 1 to 23 and Comparative Examples 1 to 14. The temperature of the etchant composition was set at 30 ° C. during the etching process. When the temperature reached 30 ± 0.1 ° C., the etching process of the test piece was performed for 60 seconds Lt; / RTI > After washing and drying, the cross-section was measured using an electron microscope (SEM; model: SU-8010, manufactured by Hitachi), and it was confirmed whether or not molybdenum alloy or titanium had penetrated into the upper copper film. , And the results are shown in Tables 4 and 5 below.

Experimental Example  4. One side Etching amount  evaluation

A hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a molybdenum titanium alloy film (MoTi), and a hydrogenated amorphous silicon layer (Cu) were sequentially deposited on the substrate. As another sample, a hydrogenated amorphous silicon layer (a-Si: H), a hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a titanium film (Ti) , And copper (Cu) were sequentially deposited. Thereafter, a photoresist (PR) having a predetermined pattern was formed through a photolithography process.

The two samples were subjected to an etching process using each of the etching liquid compositions of Examples 1 to 23 and Comparative Examples 1 to 14. The temperature of the etchant composition was set at 30 ° C. during the etching process. When the temperature reached 30 ± 0.1 ° C., the etching process of the test piece was performed for 60 seconds Lt; / RTI > After washing and drying, side etch lengths were confirmed using an electron microscope (SEM; model name: SU-8010, manufactured by Hitachi) and evaluated according to the evaluation criteria of Table 3. The results are shown in Tables 4 and 5 Table 5 shows the results.

Experimental Example  5. Residue evaluation

A hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a molybdenum titanium alloy film (MoTi), and a hydrogenated amorphous silicon layer (Cu) were sequentially deposited on the substrate. As another sample, a hydrogenated amorphous silicon layer (a-Si: H), a hydrogenated amorphous silicon layer (n + a-Si: H) doped with phosphorus (P), a titanium film (Ti) , And copper (Cu) were sequentially deposited. Thereafter, a photoresist (PR) having a predetermined pattern was formed through a photolithography process.

The two samples were subjected to an etching process using each of the etching liquid compositions of Examples 1 to 23 and Comparative Examples 1 to 14. The temperature of the etchant composition was set at 30 ° C. during the etching process. When the temperature reached 30 ± 0.1 ° C., the etching process of the test piece was performed for 60 seconds Lt; / RTI > After cleaning and drying, the etched surfaces were measured using an electron microscope (SEM; model: SU-8010, manufactured by Hitachi), and it was confirmed whether or not the copper film remained unremoved and evaluated according to the evaluation criteria of Table 3 , And the results are shown in Tables 4 and 5 below.

Experimental Example  6. Explosion Assessment

Each of the etching composition compositions of Examples 1 to 23 and Comparative Examples 1 to 14 was stored in a thermostatic chamber after the production and the temperature was measured at the same time. The temperature was measured for 24 hours and the occurrence of a phenomenon showing a fever or aggravation reaction of 30 ° C or more was observed and evaluated according to the evaluation criteria of Table 3. The results are shown in Tables 4 and 5 below.

division Great usually Bad Remarks ◎ ○ X Longitudinal etching rate Cu 80 Å / sec or more to 130 Å / sec or less 130 Å / sec to 150 Å / sec or less Less than 80 ANGSTROM / sec, more than 150 ANGSTROM / sec Means the thickness of the etched layer per second MoTi alloy 5 Å / sec or more to 15 Å / sec or less 15 A / sec to less than 20 A / sec Less than 5 A / sec, more than 20 A / sec Ti 5 Å / sec or more to 10 Å / sec or less 10 Å / sec or more to 20 Å / sec or less Less than 5 A / sec, more than 20 A / sec Hydrogenated a-Si 8 Å / sec or more More than 4 Å / sec to less than 8 Å / sec Less than 4 Å / sec pH pH 3 or less Above pH 3 Overeating angle (erosion) MoTi Not occurring Occur Etch generation criterion inside wiring relative to upper Cu Ti Not occurring Occur Unilateral etching amount 1 μm or less More than 1 μm and not more than 1.5 μm Above 1.5 탆 The width from PR to Cu wiring in the lateral direction Residue MoTi Not occurring Occur The presence or absence of metal residue in the etched area Ti Not occurring Occur explosion Not occurring Occur A reaction or explosion of 50 ° C or more.

division Longitudinal etching rate pH Overeating angle (erosion) Unilateral etching amount Residue explosion Cu MoTi alloy Ti Hydrolyzed a-Si
(a-Si: H) MoTi Ti MoTi Ti Example 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 6 ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 11 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 12 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 13 ○ ○ ○ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 14 ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 15 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 16 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 17 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 18 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 19 ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 20 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 21 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 22 ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 23 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

division Longitudinal etching rate pH Overeating angle (erosion) Unilateral etching amount Residue explosion Cu MoTi alloy Ti Hydrolyzed a-Si MoTi Ti MoTi Ti Comparative Example 1 X X X X X ◎ ◎ ◎ X X ◎ Comparative Example 2 X ○ ○ ◎ ◎ ◎ ◎ X ◎ ◎ X Comparative Example 3 X ◎ ◎ ◎ X ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 4 X ◎ ◎ ◎ ◎ ◎ ◎ ◎ X X ◎ Comparative Example 5 ◎ ◎ ◎ ◎ ◎ X X X ◎ ◎ ◎ Comparative Example 6 ◎ X X ◎ ◎ ◎ ◎ ◎ X X ◎ Comparative Example 7 X X X ◎ ◎ X X X ◎ ◎ ◎ Comparative Example 8 X X X ◎ ◎ ◎ ◎ ◎ X X ◎ Comparative Example 9 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X Comparative Example 10 X X X ◎ ◎ ◎ ◎ ◎ X X ◎ Comparative Example 11 ◎ X X X ◎ ◎ ◎ ◎ X X ◎ Comparative Example 12 ◎ ◎ ◎ ◎ ◎ X X ◎ ◎ ◎ ◎ Comparative Example 13 ◎ ◎ ◎ X ◎ ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 14 X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X

Claims (10)

10 to 35% by weight of hydrogen peroxide,
0.5 to 5% by weight of organic acid,
0.1 to 5% by weight of phosphoric acid or phosphate,
0.1 to 5% by weight of a water-soluble cyclic amine compound,
0.1 to 5% by weight of a water-soluble compound having an amino group and a carboxylic acid group in one molecule,
0.01 to 0.9% by weight of a fluorine compound,
0.01 to 2% by weight of noble metal compound, and
Water-containing
Copper based metal film and silicon layer etchant composition. The method according to claim 1,
The organic acid may be selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, And at least one selected from the group consisting of hydrofluoric acid, hydrofluoric acid, and pentanoic acid. The method according to claim 1,
The water-soluble cyclic amine compound may be an aminotetrazole, an imidazole, an indole, a purine, a pyrazole, a pyridine, a pyrimidine, a pyrrole, Wherein the etching solution composition is at least one selected from the group consisting of pyrrolidine, quinolone, and pyrroline. The method according to claim 1,
The water-soluble compound having an amino group and a carboxylic acid group in the above-mentioned molecule may be selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid nitrilotriacetic acid, and sarcosine. < RTI ID = 0.0 > 8. < / RTI > The method according to claim 1,
The fluorine compound is preferably selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride. And at least one member selected from the group consisting of the above-mentioned components. The method according to claim 1,
Wherein the noble metal compound is at least one selected from the group consisting of copper, silver, and gold. The method according to claim 1,
The copper-based metal film may be a single film of copper or a copper alloy; or
A copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer; a copper molybdenum alloy film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer; a copper layer formed on the titanium layer; Or a copper-titanium alloy film comprising a titanium alloy layer and a copper layer formed on the titanium alloy layer. 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 source and drain electrodes on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The step a) includes forming a copper-based metal film on the substrate and etching the copper-based metal film with the etchant composition to form a gate wiring,
The step d) includes forming a copper-based metal film and etching the copper-based metal film with an etchant composition to form source and drain electrodes,
Wherein the etchant composition comprises 10 to 35 wt% of hydrogen peroxide, 0.5 to 5 wt% of organic acid, 0.1 to 5 wt% of phosphoric acid or phosphate, 0.1 to 5 wt% of a water-soluble cyclic amine compound, A water-soluble compound having an acid group in an amount of 0.1 to 5 wt%, a fluorine compound in an amount of 0.01 to 0.9 wt%, a noble metal compound in an amount of 0.01 to 2 wt%, and a water balance. The method of claim 8,
Wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate. The method of claim 8,
The copper-based metal film may be a single film of copper or a copper alloy; or
A copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer; a copper molybdenum alloy film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer; a copper layer formed on the titanium layer; Wherein the copper-titanium alloy film is a copper-titanium alloy film including a titanium alloy film and a copper layer formed on the titanium alloy layer.