TWI658123B - 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

The invention provides an etching solution composition for a copper layer and a titanium layer and a method for manufacturing an array substrate for a liquid crystal display using the same. The composition of the etching solution for etching the copper layer and the titanium layer includes persulfate, a chlorine compound, a copper salt, a cyclic amine compound, and an electron donating compound, so that the copper layer and the titanium layer can be etched in batches at a high etching rate, and at the same time, Prevents poorly soluble precipitation.

Description

Etching solution composition for copper layer and titanium layer and method for preparing array substrate for liquid crystal display using the same Background of the invention

The present invention relates to an etching solution composition for a copper layer and a titanium layer and a method for manufacturing an array substrate for a liquid crystal display using the same.

A representative electronic circuit for driving a semiconductor device and a flat panel display is a thin film transistor (TFT). A method of manufacturing a TFT-LCD generally includes forming a metal film for a gate and source / drain electrode wiring material on a substrate, forming a photoresist on a selected region of the metal film, and then using the photoresist The agent serves as a photomask to etch the metal film.

Conventionally, as a wiring material for a gate electrode and a source / drain electrode, a metal film in which aluminum or its alloy and another metal have been sequentially laminated has been used. Aluminum is cheaper and has low resistance, but does not have good chemical resistance, which may cause problems in the operation of the liquid crystal panel, for example, it may be shorted from other conductive layers due to failures such as small bumps in post-processing, or it may be with oxides The layers are in contact to form an insulating layer.

In view of the foregoing, a double metal film having a copper layer and a titanium layer has been proposed as Wiring material for gate and source / drain electrodes.

However, the above technology involves such a problem: in order to etch a dual metal film having a copper layer and a titanium layer, two different etchantes for etching the two metal films must be used. Specifically, in order to etch a copper-containing copper film, an etchant based on hydrogen peroxide or potassium persulfate is generally used.

Korean Patent Laid-Open Publication No. 2010-0040352 discloses a hydrogen peroxide etchant including hydrogen peroxide, phosphoric acid, phosphate, a chelating agent, and a cyclic amine compound. However, the hydrogen peroxide etchant includes disadvantages such as self-decomposition of the composition caused by the occurrence of "disproportionation" or instability due to rapid changes in the composition over time.

Specifically, the cyclic amine compound is combined with copper ions generated during the etching of the copper film. In this case, when chloride ions are present in the etchant, a poorly soluble precipitate may occur due to a reaction between the chloride ions and the combined substance.

In addition, potassium persulfate etchant has disadvantages such as low etching speed and instability over time.

Therefore, it is an object of the present invention to provide an etching solution composition that prevents precipitation of poor solubility even when cyclic amine compounds, copper salts, and chlorine compounds are included as components.

In addition, another object of the present invention is to provide an etching solution composition capable of uniformly etching a copper layer and a titanium layer at a high etching rate.

In addition, another object of the present invention is to provide a method for manufacturing a thin film transistor using the above-mentioned etching solution composition.

The above objectives of the present invention will be achieved by the following features:

(1) An etching solution composition for etching a copper layer and a titanium layer, comprising: a persulfate, a chlorine compound, a copper salt, a cyclic amine compound, and an electron donating compound.

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

(3) The etching solution composition according to the above (1), wherein the chlorine compound is at least one selected from the group consisting of chloric acid, sodium chloride, potassium chloride, and ammonium chloride.

(4) The etching solution composition according to the above (1), wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate, and copper ammonium phosphate.

(5) The etching solution composition according to the above (1), wherein the cyclic amine compound includes a compound selected from the group consisting of a triazole compound, an aminotetrazole compound, an imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, and a pyrimidine At least one of a group consisting of a compound, a pyrrole compound, a pyrrolidine compound, and a pyrroline compound.

(6) The etching solution composition according to the above (1), wherein the electron-donating compound includes at least one selected from the group consisting of glutamic acid, rosin acid, aminobenzenesulfonic acid, riboflavin, folic acid, and gallic acid And at least one of the group consisting of potassium, sodium, and ammonium salts thereof; and selected from the group consisting of L-isoleucine, adipic acid, palmitic acid, maleic acid, diethylene triamine pentaacetic acid, At least one of the group consisting of N-acetamyl-L-cysteine and L-methionine and its potassium, sodium and ammonium salts.

(7) The etching solution composition according to the above (1), comprising: 0.5% to 20% by weight persulfate, 0.1% to 5% by weight of a chlorine compound, and 0.05% to 3% by weight of a copper salt , 0.5% to 5% by weight of a cyclic amine compound, 0.1% to 5% by weight of an electron donating compound, and water as the rest.

(8) The etching solution composition according to the above (1), further comprising a member selected from the group consisting of a fluorine compound, At least one of a group consisting of an inorganic acid (salt) and an organic acid (salt).

(9) The etching solution composition according to the above (8), wherein the fluorine compound includes a member selected from the group consisting of fluoric acid, ammonium fluoride, acid ammonium fluoride, ammonium fluoborate, potassium fluoride, potassium acid fluoride, and fluoboric acid. At least one of the group consisting of potassium, sodium fluoride, sodium acid fluoride, aluminum fluoride fluoboric acid, lithium fluoride, and calcium fluoride.

(10) The etching solution composition according to the above (8), wherein the inorganic acid (salt) includes a group selected from the group consisting of at least one of nitric acid, sulfuric acid, phosphoric acid, boric acid, and potassium salts, sodium salts, and ammonium salts thereof. At least one.

(11) The etching solution composition according to (8) above, wherein the organic acid (salt) includes a material selected from the group consisting of acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, and valeric acid , Sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitrate, At least one of the group consisting of acrylic acid and imminodiacetic acid and at least one of its potassium, sodium and ammonium salts.

(12) The etching solution composition according to the above (1), wherein the copper layer is a single copper layer or includes at least one selected from the group consisting of aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten, and vanadium, and copper .

(13) The etching solution composition according to the above (1), wherein the titanium layer is a single titanium layer.

(14) The etching solution composition according to the above (1), wherein the copper layer and the titanium layer are multilayers in which the copper layer and the titanium layer are alternately laminated at least once.

(15) A method of forming a metal wiring pattern, comprising: etching a copper layer and a titanium layer using the etching solution composition according to any one of (1) to (14) above.

(16) A method of manufacturing an array substrate for a liquid crystal display device, including: (a) in the insulation A gate metal layer including a lower gate metal layer and an upper gate metal layer is formed on the edge substrate; (b) the gate metal layer is etched to form a gate line including a gate electrode; (c) on the gate line Forming a gate insulating film; (d) sequentially forming a first amorphous silicon layer, a second amorphous silicon layer, a lower data metal layer, and an upper data metal layer on the gate insulation film; (e) etching the first non-silicon layer; Crystalline silicon layer, the second amorphous silicon layer, the lower data metal layer and the upper data metal layer to form a data line including a semiconductor, a resistive contact layer and a source electrode, and a drain electrode; (f) in the data Forming a protective film on the wire, the drain electrode and the gate insulating film; and (g) forming a pixel electrode connected to the drain electrode on the protective film, wherein the etching in step (b) and the etching in step (e) Etching is performed using the etching solution composition according to any one of the above (1) to (14).

(17) The method according to the above (16), wherein the lower gate metal layer or the lower data metal layer is formed of a titanium layer, and the upper gate metal layer or the upper data metal layer is formed of a copper film.

(18) The method according to the above (17), wherein the upper metal layer and the lower metal layer are simultaneously etched by using the etching solution composition.

The etching solution composition of the present invention includes an electron-donating compound, so that even when a cyclic amine compound, a copper salt, and a chlorine compound are included, it is possible to prevent a poorly soluble precipitation from occurring.

In addition, the etching solution composition of the present invention achieves uniform batch etching of a multiple metal film having a copper layer and a titanium layer at a high etching rate, thereby simplifying the etching process, improving yield, and ensuring excellent etching characteristics.

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

The above description of the present invention will be more clearly understood from the following embodiments in combination with the accompanying drawings. And other objectives, features, and other advantages, among which: FIG. 1 is a photograph for evaluating the occurrence of precipitation according to Example 5 of the present invention; and FIG. 2 is a photograph for evaluating the occurrence of precipitation according to Comparative Example 1 of the present invention.

The invention discloses an etching solution composition for a copper layer and a titanium layer, which includes a persulfate, a chlorine compound, a copper salt, a cyclic amine compound, and an electron donating compound, so that the copper layer can be etched in batches at a high etching rate and A titanium layer, while preventing poorly soluble precipitation; and a method for manufacturing an array substrate for a liquid crystal display using the same.

Hereinafter, illustrative specific examples of the present invention will be described in detail.

In this text, "a copper layer and a titanium layer" means a multiple metal film in which a copper layer and a titanium layer are laminated. Specifically, the copper layer and the titanium layer may include a double metal film in which a copper film / titanium layer is laminated in this order, and a double metal film in which a titanium layer / copper layer is laminated in this order. In addition, the copper layer and the titanium layer may include multiple metal films in which the copper layer and the titanium layer are alternately laminated in three layers or more, such as a triple metal film having three laminated copper films / titanium layers / copper films; A triple metal film having three laminated titanium layers / copper films / titanium layers; a multiple metal film having a copper film / titanium layer / copper film / titanium layer / copper layer laminated in this order or the like. Herein, the thickness of each of the copper layer and the titanium layer is not particularly limited.

In addition, in the present invention, a "copper film" may include a single copper layer made of only copper, and include a material selected from the group consisting of aluminum (Al), magnesium (Mg), manganese (Mn), beryllium (Be), A copper alloy layer of at least one of a group consisting of hafnium (Hf), niobium (Nb), tungsten (W), vanadium (V), and copper.

In addition, in the present invention, the "titanium layer" may include only titanium Made of a single titanium layer.

The persulfate salt included in the etching solution composition of the present invention is a main component for etching a copper film and is also a component involved in etching a titanium layer. Specific examples thereof may 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 ) or the like, which may be It is used alone or in combination of two or more kinds thereof.

Persulfate can be included in an amount of 0.5% to 20% by weight ("wt.%") And preferably 5wt.% To 18wt.% Of the total weight of the etching solution composition. Within this content range, the copper layer can be etched to a desired degree and provide excellent etching characteristics. If its content is less than 0.5 wt.%, The copper layer may not be etched or etched at a reduced etch rate. When the content exceeds 20 wt.%, The etching rate becomes high and difficulties are encountered in the control method, and thus the copper layer and the titanium layer may be over-etched.

Chlorine compounds mean compounds which dissociate in water to produce chloride ions. Chlorine compounds are auxiliary oxidants for etching copper or metal films including copper, and can be used to control the angle of the cone. Specific examples thereof may include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH ₄ Cl), and the like, which may be used alone or in combination of two or more kinds thereof.

The chlorine compound may be included in an amount of 0.1 wt.% To 5 wt.%, And preferably 0.5 wt.% To 3 wt.%, Of the total weight of the etching solution composition. Within this content range, the copper layer can be etched to a desired degree and provide excellent etching characteristics. If its content is less than 0.1 wt.%, The copper layer can be etched at a reduced etch rate, thereby causing deterioration of the etching characteristics. When its content exceeds 5 wt.%, Excessive etching may occur and the loss of metal wiring may occur.

Copper salts can be used to control CD skew. Specific examples thereof may include copper nitrate (Cu (NO ₃ ) ₂ ), copper sulfate (CuSO ₄ ), copper ammonium phosphate (NH ₄ CuPO ₄ ), and the like (but not including persulfate), which may be used alone or in combination of the two. Or use in combination of two or more.

The copper salt may be included in an amount of 0.05 wt.% To 3 wt.% And preferably 0.1 wt.% To 2 wt.% Of the total weight of the etching solution composition. Within this content range, a significantly constant CD skew can be obtained. If its content is less than 0.05 wt.%, The deviation in the CD skew change for the number of sheets to be treated can be significantly increased. When its content exceeds 3 wt.%, The oxidation efficiency of the main oxidant decreases and the number of flakes to be treated is reduced.

The cyclic amine compound can be used to control the etching speed and reduce the CD loss of the pattern, thus increasing the profit in the method.

The cyclic amine compound is not particularly limited as long as it may include a cyclic amine compound used in any conventional art in the related art. For example, it may be any of azole compounds having 1 to 30 carbon atoms. More specifically, it may include a triazole compound, an aminotetrazole compound, an imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, a pyrroline compound, and the like, They may be used alone or in combination of two or more kinds thereof.

The triazole compound may include, for example, a mixture containing at least one kind or two or more kinds of compounds represented by the following Formula 1.

Wherein R ¹ and R ² are each independently a hydrogen atom; a carboxyl group; an amine group; a hydroxyl group; a cyano group; a formamyl group; a sulfonic acid group; Or an unsubstituted alkyl or sulfoalkyl group having 1 to 20 carbon atoms, and may include an ester group, and Q is a hydrogen atom; a hydroxyl group; a substituent represented by Formula 2 below; and An aryl or hydroxyl group of 20 carbon atoms is substituted or unsubstituted alkyl or alkoxy group having 1 to 10 carbon atoms, and may include at least one of amidino group and ester group.

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 a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, Hydroxyalkyl or alkoxyalkyl.

The compound represented by Formula 1 may include, for example, 1,2,3-benzotriazole, 5-methylbenzotriazole, 1- (2,2-dihydroxyethyl) benzotriazole, 1-hydroxyl Benzotriazole, 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- Carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, 5-carboxybenzotriazole dodecyl ester or the like. These compounds may be used alone or in combination of two or more kinds thereof.

In addition to the compound represented by Formula 1, the etching solution composition of the present invention may further include other triazole compounds commonly used in the related art. For example, 1,2,3-triazole, 1,2,4-triazole, tolyltriazole, 4-amino-1,2,4-triazole, or the like may be included. These compounds may be used alone or in combination of two or more kinds thereof.

Aminotetrazole compounds may include, for example, aminotetrazole, 5-aminotetrazole, 5-amine Phenyl-1-phenyltetrazole, 5-amino-1 (1-naphthyl) tetrazole, 1-methyl-5-aminotetrazole, 1,5-diaminotetrazole, or the like. Preferably, aminotetrazole is used.

Imidazole compounds may include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole, They may be used alone or in combination of two or more kinds thereof.

Indole compounds may include, for example, aminoalkylindole, benzamidineindole, methylindole, phenylethinoindole, indolecarbazole, or the like, which may be used alone or in combination It can be used in combination of two or more kinds.

Purine compounds may include, for example, 6-dimethylaminopurine, 2,6-dichloro-7-methyl-7H-purine, 6- (γ, γ-dimethylallylamino) purine, 2 -Amino-6-chloro-9H-purine-9-acetic acid or the like, which may be used alone or in combination of two or more kinds thereof.

Pyrazole compounds may include, for example, 3-phenyl-1H-pyrazole, 3- (aminomethyl) pyrazole, 5- (2-thienyl) pyrazole, 1- (2-hydroxyethyl) -pyridine Azole, 3- (2-thienyl) pyrazole, 5-methyl-1H-pyrazole, 5-methyl-1H-pyrazole, 4-nitro-1H-pyrazole, 1H-pyrazole-5- Boric acid or an analog thereof may be used alone or in combination of two or more kinds thereof.

The pyridine compound may include, for example, 4- (aminoethyl) pyridine, 2- (methylamino) pyridine, pyridine trifluoroacetate, pyridine-4-acetamidamine, 2-[(pyridine-3-carbonyl)- Amino] -benzoic acid or the like, which may be used alone or in combination of two or more kinds thereof.

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

Pyrrole compounds may include, 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 or more of them Use in combination.

Pyrrolidine compounds may include, for example, 1- (2-aminoethyl) pyrridine, pyrrolidine-3-carboxylic acid, pyrrolidine-3-carboxylic acid hydrochloride, pyrrolidine-1,2-dicarboxylic acid1 -A phenyl ester or an analog thereof, which may be used alone or in a combination of two or more kinds thereof.

Pyrroline compounds may include, for example, 3-pyrroline, 2-methyl-1-pyrroline, 1-benzyl-3-pyrroline, or the like, which may be used alone or in combination of two or more of them Use of forms.

The cyclic amine compound may be included in an amount of 0.5 wt.% To 5 wt.%, And preferably 1 wt.% To 4 wt.%, Of the total weight of the etching solution composition. Within this content range, it is possible to maintain an appropriate etching rate to provide excellent etching characteristics. If its content is less than 0.5 wt.%, The etching rate of copper may be uncontrolled and excessive etching may occur. When its content exceeds 5 wt.%, The etching rate of the copper-based metal layer is greatly reduced, resulting in a significant increase in processing time.

The electron-donating compound prevents poorly soluble precipitation by bonding a chloride ion derived from a chlorine compound to a positively charged (+ electric) region of a copper ion combined by a coordination bond (chelation) with a cyclic amine compound. Specifically, the electron-donating compound provides electrons to the positively charged region, and thus prevents the combination of chloride ions.

As the electron-donating compound, at least one of a cyclic organic compound and an acyclic organic compound can be used.

The cyclic organic compound may include at least one compound selected from the group consisting of glutamic acid, rosin acid, aminobenzenesulfonic acid, riboflavin, folic acid, and gallic acid, or at least one compound selected from the group consisting of organic acids ) Of potassium, sodium and ammonium salts. As typical examples of the salt compound, there may be potassium L-ascorbate, calcium L-ascorbate, sodium L-ascorbate, and the like analog.

The non-cyclic organic compound may include at least one selected from the group consisting of L-isoleucine, adipic acid, palmitic acid, maleic acid, diethylene triamine pentaacetic acid, N-acetylfluorenyl-L-cysteine Compounds consisting of amino acids and L-methionine, or at least one compound selected from the group consisting of potassium salts, sodium salts and ammonium salts of the compounds selected from the organic acids.

Preferred examples of the electron-donating compound may include a compound selected from riboflavin, folic acid, gallic acid, ascorbic acid, diethylene triamine pentaacetic acid, N-acetamido-L-cysteine, and L-methionine. , At least one of the group consisting of potassium L-ascorbate, calcium L-ascorbate, and sodium L-ascorbate.

The electron-donating compound may be included in an amount of 0.1 wt.% To 5 wt.%, And preferably 0.3 wt.% To 3 wt.%, Of the total weight of the solution composition. If its content is less than 0.1 wt.%, A poorly soluble precipitate is highly likely to occur. When the content thereof exceeds 5 wt.%, The etching performance of the etching solution composition may be deteriorated.

If necessary, the etching solution composition of the present invention further includes at least one selected from the group consisting of a fluorine compound, an inorganic acid (salt), and an organic acid (salt).

A fluorine compound means a compound that dissociates in water to generate fluoride ions. The fluorine-containing compound is a component that etches the titanium layer and is used to remove residues generated from the titanium layer.

Specific examples of the fluorine compound may include hydrofluoric acid, ammonium fluoride, ammonium acid fluoride, ammonium fluoborate, potassium fluoride, potassium acid fluoride, potassium fluoborate, sodium fluoride, sodium acid fluoride, fluoride Aluminum, boron fluoride, lithium fluoride, and calcium fluoride can be used alone or in combination of two or more kinds thereof.

The fluorine compound may be included in an amount of 0.01 wt.% To 2 wt.%, And preferably 0.1 wt.% To 1 wt.%, Of the total weight of the etching solution composition. If its content is less than 0.01wt.%, Then Etch residue may still be present. When its content exceeds 2.0 wt.%, The etching rate of other layers such as a substrate may be increased.

In the present invention, the inorganic acid (salt) includes an inorganic acid, a salt of an inorganic acid, or both of an inorganic acid and a salt thereof. Inorganic acids (salts) are auxiliary oxidants used to etch copper and titanium layers. The etching rate can be controlled according to the content of the inorganic acid (salt) in the etching solution composition. In addition, an inorganic acid (salt) may react with copper ions in the etching solution composition, and thus it is possible to prevent an increase in copper ions and thus prevent a decrease in the etching rate.

Specific examples of the inorganic acid (salt) may include 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 alone or in combination of two or more kinds thereof.

The inorganic acid (salt) may be included in an amount of 1 wt.% To 10 wt.%, And preferably 2 wt.% To 7 wt.%, Of the total weight of the etching solution composition. Within this content range, the copper layer and the titanium layer can be suitably etched and have excellent etching characteristics. If its content is less than 1 wt.%, The etching rate may be reduced with poor etching characteristics or residues remaining. When its content exceeds 10wt.%, Over-etching or cracks may occur in the photoresist, and the etching solution composition can penetrate into the cracks, resulting in over-etching of the copper layer or titanium layer placed under the photoresist. .

In the present invention, the organic acid (salt) includes organic acids, salts of organic acids, or both organic acids and salts thereof. An organic acid (salt) is a component that is adsorbed on the surfaces of the copper layer and the titanium layer to improve the etching uniformity and achieve constant maintenance of the etching characteristics, while maintaining the flakes to be treated over time to achieve the required side etching. In addition, it can affect the increase in solubility and increase the number of processed flakes. In addition, the salt of the organic acid acts as a chelating agent to form a complex with the copper ions in the etching solution composition in order to control the etching speed of copper, and thus increase the number of treated flakes.

Specific examples of the organic acid (salt) may include a member selected from the group consisting of acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, sulfonated succinic acid, Sulfophthalic acid, salicylic acid, sulfosalicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid, imidic acid At least one of the group consisting of acetic acid, ethylenediaminetetraacetic acid (EDTA) and the above-mentioned organic acid salt. Its salts may include, for example, potassium, sodium and ammonium salts. These may be used alone or in combination of two or more kinds thereof.

The organic acid (salt) may be included in an amount of 0.1 wt.% To 10 wt.%, And preferably 1 wt.% To 8 wt.%, Of the total weight of the etching solution composition. Within this content range, the copper and titanium layers can be etched at a suitable rate and have excellent etch characteristics. If its content is less than 0.1 wt.%, The etching speed is reduced to have poor etching characteristics and a residue remains. When the content exceeds 10 wt.%, Over-etching may occur and lead to an increase in side etching, and it is impossible to achieve the effect of increasing the number of processed flakes.

In addition to the content of other components, water can be added to the etching solution composition of the present invention in a balance of 100 wt.% Of the total weight of the composition. Although the water used herein is not particularly limited, it is preferable to use deionized water. More preferably, the resistivity is 18MΩ. cm or 18MΩ. For deionized water above cm, this resistivity indicates the degree to which ions are removed from the water.

The etching solution composition of the present invention may further include any conventional additives other than the above-mentioned components. Such conventional additives may include, for example, an etching adjuster, a metal ion chelator, a corrosion inhibitor, a surfactant, a pH adjuster, or the like, but it is not limited thereto.

The etching solution composition of the present invention having the above configuration can not only etch a double metal film in which a copper layer and a titanium layer are sequentially laminated in batches at a high etching rate, but also can uniformly distribute A multiple metal film in which the above-mentioned layers are laminated two or more times is batch-etched while preventing poorly soluble precipitation. Therefore, the etching method can be simplified, the yield can be improved, and excellent etching characteristics can be secured.

In addition, the present invention provides a method for forming a metal wiring pattern by etching a copper layer and a titanium layer using the etching solution composition of the present invention. Such a method for forming a metal wiring can be effectively applied to manufacture a thin film transistor array substrate. Such thin film transistor array substrates can be applied to fabricate array substrates for liquid crystal displays, memory semiconductor display panels, or the like.

Therefore, the present invention provides a method for manufacturing an array substrate for a liquid crystal display by using the above-mentioned etching solution composition. More specifically, when a copper layer and a titanium layer are used as the gate line or the data line and the drain electrode, the above-mentioned etching solution composition can be used in the etching for preparing the same.

According to a specific example of the present invention, a method of manufacturing an array substrate for a liquid crystal display device may include the following steps: (a) forming a gate metal layer including a lower gate metal layer and an upper gate metal layer on an insulating substrate; (b) etching the gate metal layer to form a gate line including a gate electrode; (c) forming a gate insulating film on the gate line; (d) sequentially forming a first amorphous on the gate insulating film A silicon layer, a second amorphous silicon layer, a lower data metal layer, and an upper data metal layer; (e) etching the first amorphous silicon layer, the second amorphous silicon layer, the lower data metal layer, and the upper data metal Layer to form a data line including a semiconductor, a resistive contact layer, and a source electrode, and a drain electrode; (f) forming a protective film on the data line, the drain electrode, and the gate insulating film; and (g) forming The pixel electrode is connected to the drain electrode on the protective film.

In the method of manufacturing an array substrate for a liquid crystal display, the etching in step (b) and the etching in step (e) may be performed using the above-mentioned etching solution composition of the present invention.

As a preferred embodiment, the lower gate metal layer or the lower data metal layer is formed of a titanium layer, and the upper gate metal layer or the upper data metal layer is formed of a copper film. In this case, the upper metal layer and the lower metal layer are simultaneously etched by using the etching solution composition of the present invention, and thus it is possible to more simply manufacture the array substrate.

Korean Patent Laid-Open Publication No. 2012-0111636 describes a specific configuration of a method for manufacturing an array substrate for a liquid crystal display device, and the contents thereof are incorporated herein by reference.

Hereinafter, preferred specific examples are proposed to describe the present invention more specifically. However, the following examples are given only to illustrate the present invention, and those skilled in the art will clearly understand that various changes and modifications are possible within the scope and spirit of the present invention. Such changes and modifications are appropriately included in the scope of the attached patent application.

Examples

An etching solution composition (unit: wt.%) Was prepared by using the composition of the structure listed in Table 1 below.

Experimental example

1. Evaluation of precipitation

For the etching solution compositions of Examples 1 to 11 and Comparative Example 1 according to the present invention, the evaluation of the occurrence of precipitation was performed as follows.

3000 ppm of Cu powder was added to the prepared etching solution composition, and completely dissolved by using a stirrer for 30 minutes. Subsequently, the mixture was introduced into the prepared PE bottle, and the presence of precipitation was observed while storing it under harsh conditions such as low temperature (-9 ° C or below). The results are shown in Table 2 below.

2. Evaluation of etching performance

For the etching solution compositions of Examples 1 to 11 and Comparative Example 1 according to the present invention, the evaluation of the etching performance was performed as follows.

A substrate is prepared, wherein a SiNx layer is disposed on glass, a titanium layer is disposed on the SiNx layer, and a copper layer is disposed on the titanium layer. Subsequently, a photoresist pattern in a desired form is formed on the copper layer, and the substrate having the patterned photoresist is cut into samples each having a size of 550 mm × 650 mm by using a diamond blade.

The etching solution compositions prepared in Examples 1 to 11 and Comparative Example 1 were placed in a test apparatus in an injection etching mode, and heated to a temperature of 25 ° C. Subsequently, after the temperature reaches 30 ± 0.1 ° C, an etching process is performed. During the total etch time of the reference end point detector (EPD) time, a 200% overetch is performed. Each sample was introduced into the test instrument, after which injection was initiated. After the etching is completed, the treated sample is removed from the instrument, washed with deionized water, dried using a hot air dryer, and removed from the dried sample using a photoresist stripper. After washing and drying, the samples were subjected to evaluation of etching characteristics by means of a scanning electron microscope (SEM).

Referring to Table 2, the etching solution composition of all the examples showed no precipitation, but the precipitation of the etching solution composition of Comparative Example 1 was confirmed. For reference, FIG. 1 illustrates evaluation of a photograph showing precipitation of Example 5, and FIG. 2 illustrates evaluation of a photograph showing precipitation of Comparative Example 1. FIG.

In addition, it can be seen that when an electron-donating compound is further added, the etching efficiency is not deteriorated.

Claims (16)

An etching solution composition for etching a copper layer and a titanium layer, comprising: 0.5% to 20% by weight of persulfate, 0.1% to 5% by weight of a chlorine compound, and 0.05% to 3% by weight of copper Salt, 0.5% to 5% by weight of a cyclic amine compound, 0.1% to 5% by weight of an electron donor compound, and water as the rest, wherein the electron donor compound is selected from the group consisting of gallic acid, ascorbic acid, potassium L-ascorbate, At least one of a group consisting of calcium L-ascorbate and sodium L-ascorbate. For example, the composition of the etching solution according to item 1 of the application, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate. For example, the composition of the etching solution of the scope of application for the patent, wherein the chlorine compound is at least one selected from the group consisting of chloric acid, sodium chloride, potassium chloride, and ammonium chloride. For example, the composition of the etching solution according to item 1 of the application, wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate, and copper ammonium phosphate. For example, the etching solution composition of claim 1 in the patent scope, wherein the cyclic amine compound includes a compound selected from the group consisting of a triazole compound, an aminotetrazole compound, an imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, and a pyrimidine compound At least one of the group consisting of pyrrole compound, pyrrolidine compound, and pyrroline compound. For example, the etching solution composition according to claim 1 of the patent application scope further includes at least one selected from the group consisting of a fluorine compound, an inorganic acid (salt), and an organic acid (salt). For example, the composition of an etching solution according to item 6 of the application, wherein the fluorine compound includes a member selected from the group consisting of fluoric acid, ammonium fluoride, acid ammonium fluoride, ammonium fluoroborate, potassium fluoride, potassium acid fluoride, and potassium fluoroborate. At least one of the group consisting of sodium fluoride, sodium acid fluoride, aluminum fluoride, fluoboric acid, lithium fluoride, and calcium fluoride. For example, the composition of an etching solution according to item 6 of the patent application, wherein the inorganic acid (salt) includes at least one selected from the group consisting of at least one of nitric acid, sulfuric acid, phosphoric acid and boric acid and its potassium salt, sodium salt and ammonium salt. One. For example, the composition of an etching solution according to item 6 of the application, wherein the organic acid (salt) includes a material selected from the group consisting of acetic acid, butyric acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, Sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, acrylic acid And at least one of the group consisting of at least one of iminodiacetic acid and its potassium, sodium, and ammonium salts. For example, the composition of the etching solution according to item 1 of the application, wherein the copper layer is a single copper layer or includes at least one selected from the group consisting of aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten, and vanadium, and copper. For example, the composition of the etching solution of the scope of application for item 1 wherein the titanium layer is a single titanium layer. For example, the composition of the etching solution of the scope of application for the first item, wherein the copper layer and the titanium layer are multiple layers in which the copper layer and the titanium layer are alternately laminated at least once. A method for forming a metal wiring pattern, comprising: etching a copper layer and a titanium layer using an etching solution composition such as any one of items 1 to 12 of a patent application scope. A method for manufacturing an array substrate for a liquid crystal display device, comprising: (a) forming a gate metal layer including a lower gate metal layer and an upper gate metal layer on an insulating substrate; (b) etching the gate metal Layer to form a gate line including a gate electrode; (c) forming a gate insulating film on the gate line; (d) sequentially forming a first amorphous silicon layer and a second amorphous silicon layer on the gate insulating film Layer, lower data metal layer and upper data metal layer; (e) etching the first amorphous silicon layer, the second amorphous silicon layer, the lower data metal layer, and the upper data metal layer to form a semiconductor, resistance contact Layer and source electrode data line, and drain electrode; (f) forming a protective film on the data line, the drain electrode, and the gate insulating film; and (g) forming a pixel electrode, which is connected to the protection The drain electrode on the film, wherein the etching of step (b) and the etching of step (e) are performed using an etching solution composition as described in any one of claims 1 to 12 of the patent application scope. For example, the method of claim 14 in which the lower gate metal layer or the lower data metal layer is formed of a titanium layer, and the upper gate metal layer or the upper data metal layer is formed of a copper film. For example, the method of claim 15 in which the upper gate metal layer or the upper data metal layer and the lower gate metal layer or the lower data metal layer are simultaneously etched by using the etching solution composition.