TW201631216A - Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same - Google Patents

Abstract

Disclosed are an etchant composition for a copper layer and a titanium layer, and a method of manufacturing an array substrate for a liquid crystal display using the same. The etchant composition of the present invention includes: 0.5 to 20 wt. % of persulfate; 0.01 to 2 wt. % of a fluorine compound; 1 to 10 wt. % of inorganic acid (salt); 5 to 20 wt. % of organic acid (salt); 0.1 to 5 wt. % of a cyclic amine compound including alkyl (having 1 to 5 carbon atoms) tetrazole; 0.1 to 10 wt. % of sulfonic acid compound; and water as the balance, thereby, it is possible to uniformly batch-etch a copper layer and a titanium layer at a high etching speed with a reduced variation in an inclined angle of the etched pattern even if the number of treated sheets is increased.

Description

Copper layer and titanium layer etching liquid composition, and method for using the same for preparing liquid crystal display display substrate

The present invention relates to a copper layer and an etchant composition of a titanium layer, and to a method of using the etchant composition to prepare a liquid crystal display array substrate.

A representative circuit for driving a semiconductor device and a flat panel display is a thin film transistor (TFT). The process for preparing a TFT-LCD generally comprises forming a metal layer on the substrate as a wiring material for the gate and the source/drain electrodes, forming a photoresist on a selected region of the metal layer, and then using the photoresist as a mask. A cover is used to etch the metal layer.

Conventionally, a metal layer in which aluminum or an alloy thereof is sequentially laminated with another metal has been used as a wiring material for a gate and a source/drain electrode. Aluminum is relatively inexpensive and has low electrical resistance, but its chemical resistance is poor, which causes operational problems of the liquid crystal panel, because defects (such as hillocks in post-treatment) are short-circuited from other conductive layers, or contact with the oxide layer to form insulation. Floor.

In view of the above, a double metal layer having a copper layer and a titanium layer has been proposed as a wiring material for a gate and a source/drain electrode.

However, the above technique involves such a problem that in order to etch a double metal layer having a copper layer and a titanium layer, it is necessary to etch the above two metal layers using two different etching liquids. In particular, in order to etch a copper-containing copper layer, an etching solution based on hydrogen peroxide or potassium hydrogen persulfate is generally used.

Korean Patent Publication No. 2010-0040352 discloses a hydrogen peroxide etching solution comprising hydrogen peroxide, phosphoric acid, a phosphate, a chelating agent, and a cyclic amine compound. However, such a hydrogen peroxide etching solution has disadvantages such as disproportionation, self-decomposition of the composition, or instability due to rapid change of the composition of the composition over time. In addition, potassium persulfate etchant has disadvantages such as low etch rate and instability over time.

Further, conventionally, the inclination angle of the etching pattern varies depending on the number of films processed by the etching liquid, so that there is a disadvantage that the life of the etching liquid cannot be increased.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an etching liquid composition which has a reduced variation in etching inclination angle even when the number of sheets to be processed is increased, and which has excellent time stability and heat suppression performance.

Another object of the present invention is to provide an etchant composition which can uniformly etch a copper layer and a titanium layer in a batch at a high etching rate.

Further, another object of the present invention is to provide a method of preparing a thin film transistor using the above etching liquid composition.

The above objects of the present invention are achieved by the following features:

(1) An etching liquid composition for etching a copper layer and a titanium layer comprising: 0.5 to 20 wt.% of a persulfate; 0.01 to 2 wt.% of a fluorine compound; and 1 to 10 wt.% Inorganic acid (salt); 5 to 20 wt.% of organic acid (salt); 0.1 to 5 wt.% of cyclic amine compound, containing alkyl (having 1 to 5 carbon atoms) tetrazole; 0.1 to 10 a wt.% sulfonic acid compound; and water as a residue.

(2) The etching liquid composition according to (1) above, which is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.

(3) The etchant composition according to (1) above, which is derived from hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, ammonium fluoroborate, potassium fluoride, potassium fluorohydride, potassium fluoroborate, sodium fluoride, At least one selected from the group consisting of sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, and calcium fluoride.

(4) The etching solution composition according to (1) above, wherein the inorganic acid (salt) is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and boric acid, and a potassium salt derived from the above inorganic acid And at least one selected from the group consisting of sodium salts and ammonium salts.

(5) The etchant composition according to (1) above, wherein the organic acid (salt) is derived from ascorbic acid, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, a group consisting of sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid and iminodiacetic acid At least one selected from the group consisting of at least one selected from the group consisting of potassium salts, sodium salts and ammonium salts of the above organic acids.

(6) The etchant composition according to (1) above, wherein the alkyltetrazole is at least selected from the group consisting of 5-methyltetrazole, 5-ethyltetrazole and 5-propyltetrazole. one of them.

(7) The etchant composition according to (1) above, wherein the cyclic amine compound is derived from a triazole compound, a tetrazole compound, an imidazole compound, an anthraquinone compound, an anthraquinone compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, At least one selected from the group consisting of a pyrrole compound, a pyrrolidine compound, and a pyrroline compound.

(8) The etchant composition according to (1) above, which is derived from sulfosalicylic acid, sulfamic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, At least one selected from the group consisting of benzenesulfonic acid, sulfamic acid and polystyrenesulfonic acid.

(9) The etching liquid composition according to (1) above, wherein the copper layer is a copper single layer or contains at least one selected from the group consisting of aluminum, magnesium, manganese, lanthanum, cerium, lanthanum, tungsten, and vanadium. One of them and copper.

(10) The etchant composition according to (1) above, wherein the titanium layer is a titanium monolayer.

(11) The etching liquid composition according to (1) above, wherein the copper layer and the titanium layer are a plurality of layers, wherein the copper layer and the titanium layer are alternately laminated at least once.

(12) A method for forming a pattern of a metal wiring comprising etching a copper layer and a titanium layer using the etching liquid composition as described in (1) to (11) above.

(13) A method for manufacturing an array substrate of a liquid crystal display, comprising: (a) forming a gate wiring on a substrate; (b) forming a gate on the substrate on which the gate wiring is formed An insulating layer; (c) forming a semiconductor layer on the gate insulating layer; (d) forming a source and drain wiring on the semiconductor layer; and (e) forming a pixel electrode connected to the drain wiring The step (d) includes forming a copper layer and a titanium layer on the semiconductor layer, and etching the copper layer and the titanium layer using the etching liquid composition as described in (1) to (11) above to form a source. With bungee wiring.

The etching liquid composition of the present invention has a variation in the etching pattern inclination angle (etching inclination angle) even when the number of processed sheets is increased to have a longer service life than the conventional etching liquid composition.

At the same time, the etching liquid composition of the present invention can perform uniform batch etching on multiple metal layers having a copper layer and a titanium layer at a high etching rate, thereby simplifying the etching process, improving productivity, and ensuring excellent etching properties.

Therefore, the etching liquid composition of the present invention can be usefully applied to the manufacture of a thin film transistor which is used for an array substrate of a liquid crystal display.

The present invention discloses an etchant composition for a copper layer and a titanium layer, and a method of manufacturing an array substrate of a liquid crystal display using the etchant composition. The etching solution composition of the present invention comprises: 0.5 to 20 wt.% of a persulfate; 0.01 to 2 wt.% of a fluorine compound; 1 to 10 wt.% of a mineral acid (salt); and 5 to 20 wt.% of Organic acid (salt); 0.1 to 5 wt.% of a cyclic amine compound comprising an alkyl group (having 1 to 5 carbon atoms) tetrazole; 0.1 to 10 wt.% of a sulfonic acid compound; and water as a residue, Thereby, a copper layer and a titanium layer can be uniformly batch-etched at a high etching rate, and even when the number of processed sheets is increased, there is a decrease in the inclination angle of the etching pattern.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In the present specification, "a copper layer and a titanium layer" means a multiple metal layer in which a laminated copper layer and a titanium layer are present. Specifically, the copper layer and the titanium layer may include a double metal layer laminated in this order of a copper layer/titanium layer, and a double metal layer laminated in this order of the titanium layer/copper layer. In addition, the copper layer and the titanium layer may comprise a multiple metal layer, wherein the copper layer and the titanium layer are alternately stacked in at least three layers, for example, a triple metal layer having three layers of a copper layer/titanium layer/copper layer; a triple metal layer of a layered titanium layer/copper layer/titanium layer; a multiple metal layer layered in the order of copper layer/titanium layer/copper layer/titanium layer/copper layer. Herein, the thickness of each of the copper layer and the titanium layer is not particularly limited.

Further, in the present invention, the "copper layer" may comprise a copper single layer made only of copper, and/or comprise from aluminum (Al), magnesium (Mg), manganese (Mn), bismuth (Be), bismuth ( At least one copper alloy layer selected from the group consisting of Hf), niobium (Nb), tungsten (W), and vanadium (V), and copper.

Meanwhile, in the present invention, the "titanium layer" is a titanium single layer made only of titanium.

The persulfate contained in the etching liquid composition of the present invention is a main component for etching the copper layer, and is also a component involved in etching the titanium layer. Specific examples thereof include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), potassium persulfate (K ₂ S ₂ O ₈ ), etc., which may be used alone or in combination. Two or more of them are used.

The persulfate may be included in an amount of 0.5 to 20 wt.%, and preferably 5 to 18 wt.%, based on the total weight of the etching liquid composition. Within this range of contents, the copper layer can be etched to the extent required and provides an excellent etch profile. If the content is less than 0.5 wt.%, the copper layer cannot be etched or may be etched at a reduced etch rate. When the content exceeds 20 wt.%, the etching rate becomes higher, and difficulties are encountered in the control process, so that the copper layer and the titanium layer may be excessively etched.

A fluorine compound refers to a compound which can be dissociated in water to generate fluorine ions. The fluorochemical is a component that etches the titanium layer and acts to remove residues from the titanium layer.

The fluorine compound may contain, for example, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, ammonium fluoroborate, potassium fluoride, potassium fluorohydride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, and fluorine. Calcium, which may be used singly or in combination of two or more thereof.

The fluorine-containing compound to be contained may be included in an amount of from 0.01 to 2.0 wt.%, and preferably from 0.1 to 1 wt.%, based on the total mass of the composition. Within this range of contents, the etching ability and the ability to suppress the generation of residues are excellent. If the content is less than 0.01 wt.%, etching residues are left. When the content exceeds 2.0 wt.%, etching of other layers such as a substrate is increased.

In the present invention, the inorganic acid (salt) contains both an inorganic acid, a salt of an inorganic acid, or both an inorganic acid and a salt thereof. The inorganic acid (salt) is an auxiliary oxidant for etching the copper layer and the titanium layer. The etching rate can be controlled according to the inorganic acid (salt) content in the etching liquid composition. Further, the inorganic acid (salt) reacts with the copper ions in the etching liquid composition, and thus the increase of the copper ions can be avoided, thereby avoiding the reduction of the etching rate.

The inorganic acid (salt) may contain, for example, nitric acid, sulfuric acid, phosphoric acid, boric acid, perchloric acid, and salts thereof. Salts of inorganic acids may include, for example, potassium, sodium and ammonium salts. These compounds may be used singly or in combination of two or more.

The content of the inorganic acid (salt) may be included in an amount of 1 to 10 wt.%, and preferably 2 to 7 wt.%, based on the total weight of the etching liquid composition. Within this content range, the copper and titanium layers can be suitably etched and have an excellent etch profile. If the content is less than 1 wt.%, the etching rate may be lowered to have a poor profile or leave a residue. When the content exceeds 10 wt.%, excessive etching may occur, or cracks may be generated in the photoresist, and the etching liquid composition may penetrate into the crack to cause excessive etching of the copper layer or the titanium layer under the photoresist.

In the present invention, the organic acid (salt) contains an organic acid, a salt of an organic acid, or both an organic acid and a salt thereof. The organic acid (salt) is a component that is absorbed on the surface of the copper layer and the titanium layer to increase etching uniformity and to maintain the uniformity of the etching profile while maintaining the treated sheet to achieve the desired side etching over time. In addition, it affects the increase in solvency to increase the number of sheets processed. Further, the salt of the organic acid acts as a chelating agent to form a complex with the copper ions in the composition of the etching solution to control the etching speed of the copper, thereby increasing the number of sheets processed.

The inorganic acid (salt) may include, for example, ascorbic acid, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, sulfosuccinic acid, sulfo-o-benzene. Dicarboxylic acid, salicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid, iminodiacetic acid and ethylenediaminetetraacetic acid (EDTA), or from the above organic acids At least one selected from the group consisting of a potassium salt, a sodium salt and an ammonium salt. These compounds may be used singly or in combination of two or more.

The organic acid (salt) may be included in an amount of 5 to 20 wt.%, and preferably 2 to 18 wt.%, based on the total weight of the etching liquid composition. Within this range of contents, the copper and titanium layers can be etched at an appropriate rate and have an excellent etch profile. If the content is less than 5 wt.%, the etching rate may be lowered to have a poor etching profile, and/or a residue may be left. When the content exceeds 20 wt.%, excessive etching occurs to cause an increase in side etching.

The cyclic amine compound in the present invention contains an alkyl group (having 1 to 5 carbon atoms) of tetrazole. The alkyltetrazole acts to uniformly etch the copper film and control its etching rate. In addition, the alkyltetrazole acts to control an initial etch tilt angle to be consistent without increasing even as the number of sheets processed increases.

The alkyltetrazole may be included in an amount of 0.1 to 4 wt.%, and preferably 1 to 4 wt.%, based on the total weight of the etching liquid composition. If the content of the alkyltetrazole is less than 0.1 wt.%, the etching tilt angle increases as the number of processed sheets increases. When the content exceeds 4 wt.%, the etching cannot be sufficiently performed, and thus an etching residue is generated.

Preferably, the alkyltetrazole is at least one selected from the group consisting of 5-methyltetrazole, 5-ethyltetrazole and 5-propyltetrazole.

The cyclic amine compound further contains other compounds different from the above alkyltetrazole. A cyclic amine compound other than the above alkyltetrazole is effective in preventing corrosion and controlling the etching rate while reducing the CD loss of the pattern, thereby increasing the marginal profit of the process.

The cyclic amine compound is not particularly limited as long as it is any compound used in the related art. For example, it may be any one of azole compounds having 1 to 30 carbon atoms. More specifically, a triazole compound, a tetrazole compound, an imidazole compound, an anthracene compound, an anthracene compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, a pyrroline compound, or the like can be used alone. Or in combination of two or more.

The triazole compound contains, for example, a mixture containing at least one or two or more compounds represented by the following formula 1.

[Formula 1] (Wherein R ¹ and R ² are each independently a hydrogen atom; carboxy; amino; hydroxy; cyano; acyl methyl; a sulfonic group; or an alkyl sulfonic acyl group having from 1 to 20 carbon atoms by the a carboxyl group, an amino group, a hydroxyl group, a cyano group, a decyl group and/or a sulfonic acid group may be substituted or unsubstituted, and R ¹ and R ² may have an ester group, and Q is a hydrogen atom; a hydroxyl group; represented by the following formula 2 a substituent; and an alkyl or alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted with an aryl or hydroxy group having 6 to 20 carbon atoms, and Q may comprise a guanamine or ester At least one of the bases.)

[Formula 2] (wherein R ³ is an alkylene group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms which are replaced or unsubstituted by a hydroxyl group, Hydroxyalkyl or alkoxy.)

The compound represented by Formula 1 contains, for example, 1,2,3-benzotriazole, 5-methylbenzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-hydroxybenzene And triazole, 1-methoxybenzotriazole, 1-(1,2-dihydroxypropyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, N, N-bis-(2-ethylhexyl)-arylmethyl-1H-benzotriazole-1-methylamine, 2,2'-{[(4-methyl-1H-benzotriazole-1 -yl)methyl]imino}diethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 5-carboxyl Benzotriazole butyl ester, 5-carboxybenzotriazol octyl ester, 5-carboxybenzotriazole dodecyl ester and the like. These compounds may be used singly or in combination of two or more kinds thereof.

The etching solution composition of the present invention may further comprise other triazole compounds which are different from those of the formula 1 which are commonly used in the related art. For example, 1,2,3-triazole, 1,2,4-triazole, tolyltriazole, 4-amino-1,2,4-triazole, and the like may be included. These compounds may be used singly or in combination of two or more kinds thereof.

The tetrazole compound includes, for example, aminotetrazole, 5-aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1-(1-naphthyl)tetrazole, 1-methyl-5-amino group. Tetrazolium, 1,5-diaminotetrazole, and the like. It is preferred to use an aminotetrazole.

The imidazole compound comprises, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole, which Used alone or in combination of two or more of them.

The hydrazine compound contains, for example, aminoalkyl hydrazine, benzoquinone, methyl hydrazine, phenethyl hydrazine, carbazole, etc., which may be used alone or in two or more of them. In conjunction with.

The ruthenium compound contains, for example, 6-dimethylaminopurine, 2,6-dichloro-7-methyl-7H-indole, 6-(γ,γ-dimethylpropenylamine) oxime, 2-amino-6- Chloro-9H-indole-9-acetic acid or the like, which may be used singly or in combination of two or more kinds thereof.

The pyrazole compound includes, for example, 3-phenyl-1H-pyrazole, 3-(aminomethyl)pyrazole, 5-(2-thienyl)pyrazole, 1-(2-hydroxyethyl)-pyrazole, 3-(2-thienyl)pyrazole, 5-methyl 1H-pyrazole, 4-nitro-1H-pyrazole, 1H-pyrazole-5-boronic acid, etc., which may be used alone or in two More or more combined.

The pyridine compound contains, for example, 4-(aminoethyl)pyridine, 2-(methylamino)pyridine, pyridine trifluoroacetate, pyridine-4-acetamide, 2-[(pyridine-3-carbonyl)-amino]- Benzoic acid, which may be used singly or in combination of two or more of them.

The pyrimidine compound contains, for example, pyrimidine-5-carboxylic acid, pyrimidine-2-carboxylic acid, or the like, which may be used singly or in combination of two or more kinds thereof.

The azole compound includes, for example, pyrrole-2-carboxylic acid, pyrrole-3-carboxylic acid, 1-(2-aminophenyl)pyrrole, 1H-pyrrole-1-propionic acid, or the like, which may be used alone or in two of them. More or more combined.

The pyrrolidine compound comprises, for example, 1-(2-aminoethyl)pyrrolidine, pyrrolidine-3-carboxylic acid, pyrrolidine-3-carboxylic acid hydrochloride, pyrrolidine-1,2-dicarboxylic acid 1-benzene. A base ester or the like which may be used singly or in combination of two or more kinds thereof.

The pyrroline compound contains, for example, 3-pyrroline, 2-methyl-1-pyrroline, 1-benzyl-3-pyrroline or the like, which may be used singly or in combination of two or more kinds thereof.

The cyclic amine compound containing a terminal tetrazole may be included in an amount of 0.1 to 5 wt.%, and preferably 0.5 to 4 wt.%, based on the total weight of the etching liquid composition. If the content is less than 0.1 wt.%, excessive CD loss occurs. When the content exceeds 5 wt.%, the etching rate of the copper metal layer is excessively reduced, thereby excessively prolonging the processing time.

The sulfonic acid compound is dissociated into sulfate ion (SO ₄ ^2- ) in the composition of the etching solution to reduce the hydrolysis rate of sulfuric acid and improve the stability over time, while avoiding the etching rate of the copper and titanium layers due to the treated sheet. The increase in amount is disturbed by the storage conditions of the etchant composition.

Specific examples of the sulfonic acid compound include sulfosalicylic acid, sulfamic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, sulfamic acid, and polystyrenesulfonic acid. These may be used singly or in combination of two or more kinds thereof.

The sulfonic acid compound may be included in an amount of 0.1 to 10 wt.%, preferably 0.5 to 5 wt.%, based on the total mass of the etching liquid composition. Within this range of contents, an optimum degree of stability over time is exhibited. If the content is less than 0.1 wt.%, the etching rate is excessively disturbed due to an increase in the number of sheets to be processed, and heat is generated when the solution is discarded after the etching is processed. When the content exceeds 10 wt.%, the stability with time is deteriorated.

The remainder of the total weight of the composition may be added to water in the etching solution composition of the present invention to achieve 100 wt.%, in addition to the contents of other components. Although the water used herein is not particularly limited, it is preferred to use deionized water. More preferably, deionized water having a resistivity of 18 MΩ•cm or more (which represents the degree of ion removal in the water) is used.

The etching liquid composition of the present invention further contains any conventional additive other than the above components. Such conventional additives may include, for example, an etching regulator, a metal ion chelating agent, a corrosion inhibitor, an interface agent, a pH adjuster, etc., but are not limited thereto.

The etching liquid composition of the present invention having the above configuration does not undergo deuteration, and thus has excellent stability with time without the component being decomposed by itself or a rapid change of its constituent components. In addition, the etchant composition of the present invention is particularly useful for uniform batch etching at rapid etch rates, not only for double metal layers of alternating layers of copper and titanium, for stacking two or more times. The same is true of the above layers. This simplifies the etching process, increases productivity, and ensures excellent etch properties.

Further, the present invention provides a method of etching a copper layer and a titanium layer by using the etching composition of the present invention to form a metal wiring pattern. This method of forming a metal wiring can be usefully applied to the fabrication of a thin film transistor array substrate. The thin film transistor (TFT) array substrate can be used for the fabrication of an array substrate of a liquid crystal display, a memory semiconductor display panel or the like.

Accordingly, the present invention provides a method of manufacturing an array substrate of a liquid crystal display by using the above etching liquid composition. More specifically, when a copper layer and a titanium layer are used as the source/drain electrodes, the above etching liquid composition is used for etching the source/drain electrodes. Further, when it is necessary to use a copper layer and a titanium layer as the pixel electrodes, the above-described etching liquid composition can also be used to etch the pixel electrodes.

A method of manufacturing a liquid crystal display array substrate according to an embodiment of the present invention includes the steps of: (a) forming a gate wiring on a substrate; (b) forming a gate on the substrate on which the gate wiring is formed; a conductive layer; (c) forming a semiconductor layer on the gate insulating layer; (d) forming a source and drain wiring on the semiconductor layer; and (e) forming a pixel connected to the drain wiring electrode.

In the manufacturing method of the liquid crystal display array substrate, the step (d) comprises forming a copper layer and a titanium layer on the semiconductor layer, and etching the copper layer and the titanium layer using the etching liquid composition according to the present invention to form Source and drain wiring.

According to the manufacturing method of the liquid crystal display array substrate having the above configuration, excellent metal wiring, that is, source/drain wiring can be easily formed, thereby achieving an increase in the size of the TFT-LCD.

In the following, preferred embodiments will be described with reference to examples to more fully understand the invention. However, it will be apparent to those skilled in the <RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt; Modifications and alternatives are of course included in the invention as defined by the scope of the appended claims. Instance

The etchant composition was prepared using the constituent components (unit: wt.%) listed in Table 1 below. [Table 1] Experimental Example 1. Etching performance

After depositing a titanium alloy layer on a glass substrate (100 mm x 100 mm), a copper layer (Ti/Cu=200/600 Å) is deposited on the above layer, and then formed on the glass substrate by optical lithography process. The pattern of the photoresist. Then, an etching process was performed using each of the etching liquid compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3. An experimental apparatus having an injection type etching mode, version 0.5 Etcher (AST), was used, and during etching, the temperature of the etching liquid composition was about 26 ° C, and an etching process was performed for 100 to 120 seconds. However, if necessary, the appropriate temperature can be adjusted based on other process conditions or parameters.

After the etching, the taper angle (°) and the side etching (micrometer) due to an increase in the number of processed sheets (copper concentration) were measured, and the results obtained are shown in Table 2 and Figs. 1 to 6 below.

For reference, the taper angle refers to the slope of the copper layer. If the taper angle is too high, cracking may occur due to poor step coverage during the next film etching, and therefore, it is important to maintain the taper angle within an appropriate range. In general, when the taper angle is increased by 10° or greater than the initial taper angle, the etchant composition used should be replaced with a new etchant composition. [Table 2]

Referring to Table 2, all of the etching liquid compositions prepared in the "Example" have excellent stability over time in terms of etching inclination angle, wherein the increase in the taper angle does not exceed 10°.

However, as can be seen from Comparative Example 1 or FIGS. 1 to 3, when ATZ is used alone, the taper angle is from the initial taper angle during the etching execution until the increased number of sheets (copper concentration) is 6000 ppm. 45.7° increases by about 15° to 60.6°. Similarly, in Comparative Example 2, the taper angle was increased by about 18 from the initial taper angle. As described above, this degree of increase in the taper angle requires replacement of the etchant composition.

Meanwhile, it can be seen from Example 2 or FIGS. 4 to 6 that when an etchant composition obtained by mixing 5-methyltetrazole (MTZ) with another cyclic amine compound (for example, 5-aminotetrazole) is used, The change in the taper angle due to the accumulation of the number of sheets processed is further significantly reduced. This represents an increase in the processing margin, and it is known that the etching liquid composition can be used even when the copper concentration reaches 6000 ppm without replacement, so that the cost can be effectively reduced.

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The above and other objects, features and other advantages of the present invention will become more <RTIgt; The etching profile of the etching solution composition at ppm; FIG. 2 is an SEM photograph illustrating the etching profile of the etching liquid composition of Comparative Example 1 at a copper concentration of 3000 ppm; FIG. 3 is an SEM photograph. The etching profile of the etching solution composition of Comparative Example 1 at a copper concentration of 6000 ppm is illustrated; FIG. 4 is an SEM photograph illustrating the etching profile of the etching liquid composition of Example 2 at a copper concentration of 0 ppm; Figure 5 is a SEM photograph illustrating the etching profile of the etchant composition of Example 2 at a copper concentration of 3000 ppm; and Figure 6 is a SEM photograph illustrating Example 2 at a copper concentration of 6000 ppm. Etching profile of the etchant composition.

Claims (13)

An etchant composition for etching a copper layer and a titanium layer comprising: 0.5 to 20 wt.% of persulfate; 0.01 to 2 wt.% of a fluorine compound; and 1 to 10 wt.% of an inorganic acid (salt); 5 to 20 wt.% of an organic acid (salt); 0.1 to 5 wt.% of a cyclic amine compound comprising an alkyl group (having 1 to 5 carbon atoms) tetrazole; 0.1 to 10 wt.% a sulfonic acid compound; and water as a residue. The etching liquid composition according to claim 1, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate. The etchant composition according to claim 1, wherein the fluorine compound is derived from fluoric acid, ammonium fluoride, ammonium hydrogen fluoride, ammonium fluoroborate, potassium fluoride, potassium fluorohydride, potassium fluoroborate, and fluorinated. At least one selected from the group consisting of sodium, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, and calcium fluoride. The etching liquid composition according to claim 1, wherein the inorganic acid (salt) is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and boric acid, and from the inorganic acid At least one selected from the group consisting of a potassium salt, a sodium salt and an ammonium salt. The etching liquid composition according to claim 1, wherein the organic acid (salt) is derived from ascorbic acid, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, and pentane. Acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid and iminodiacetic acid At least one selected from the group consisting of at least one selected from the group consisting of a potassium salt, a sodium salt and an ammonium salt of the above organic acid. The etchant composition of claim 1, wherein the alkyltetrazole is selected from the group consisting of 5-methyltetrazole, 5-ethyltetrazole and 5-propyltetrazole. At least one of them. The etching liquid composition according to claim 1, wherein the cyclic amine compound is derived from a triazole compound, a tetrazole compound, an imidazole compound, an anthraquinone compound, an anthracene compound, a pyrazole compound, a pyridine compound, or a pyrimidine. At least one selected from the group consisting of a compound, a pyrrole compound, a pyrrolidine compound, and a pyrroline compound. The etchant composition of claim 1, wherein the sulfonic acid compound is derived from sulfosalicylic acid, sulfamic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonate. At least one selected from the group consisting of acid, benzenesulfonic acid, sulfamic acid, and polystyrenesulfonic acid. The etchant composition of claim 1, wherein the copper layer is a copper single layer or comprises a group consisting of aluminum, magnesium, manganese, lanthanum, cerium, lanthanum, tungsten, and vanadium. At least one of them and copper. The etchant composition of claim 1, wherein the titanium layer is a titanium monolayer. The etchant composition of claim 1, wherein the copper layer and the titanium layer are a plurality of layers, wherein the copper layer and the titanium layer are alternately stacked at least once. A method for forming a pattern of a metal wiring, comprising etching a copper layer and a titanium layer using the etching liquid composition according to any one of claims 1 to 11. A method for manufacturing an array substrate of a liquid crystal display, comprising: (a) forming a gate wiring on a substrate; (b) forming a gate insulating layer on the substrate on which the gate wiring is formed; (c) forming a semiconductor layer on the gate insulating layer; (d) forming a source and drain wiring on the semiconductor layer; and (e) forming a pixel electrode connected to the gate wiring, wherein The step (d) includes forming a copper layer and a titanium layer on the semiconductor layer, and etching the copper layer and the titanium using the etching liquid composition according to any one of the above claims 1 to 11. Layers to form source and drain wiring.