KR20160010098A - 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 present invention relates to an etchant composition of a copper film and a titanium film, and a method of preparing an array substrate for a liquid crystal display device using the same, and more specifically, to an etchant composition of a copper film and a titanium film, and a method of preparing an array substrate for a liquid crystal display device using the same, wherein the composition can uniformly and rapidly etch a multi-metal film consisting of the copper film and the titanium film while preventing a water soluble precipitate by including persulfate, a chlorine compound, a copper salt, a cyclic amine compound, and an electron donating compound.

Description

TECHNICAL FIELD [0001] The present invention relates to an etching solution composition for a copper film and a titanium film, and a method for manufacturing an array substrate for a liquid crystal display device using the etching solution composition.

The present invention relates to an etchant composition of a copper film and a titanium film, and a method of manufacturing an array substrate for a liquid crystal display using the same.

A typical example of an electronic circuit for driving a semiconductor device and a flat panel display device is a thin film transistor (TFT). In the manufacturing process of a TFT-LCD, a metal film is usually formed as a wiring material for gate and source / drain electrodes on a substrate, a photoresist is formed in a selective region of the metal film, and the upper metal film is etched using the photoresist as a mask Process.

A metal film in which aluminum or an alloy thereof and another metal are laminated is used as a wiring material for a gate and a source / drain electrode. Aluminum is inexpensive and has low resistance, but it is not chemically stable and causes a short-circuit with other conductive layer due to defects such as hillock in the post-process, or an insulating layer due to contact with the oxide layer Thereby causing a malfunction of the liquid crystal panel.

Taking this into consideration, a double metal film of a copper film and a titanium film has been proposed as a wiring material for a gate and a source / drain electrode.

However, in order to etch the double metal film of the copper film and the titanium film, it is necessary to use two different etching solutions for etching each metal film. Particularly, in order to etch a copper film containing copper, a hydrogen peroxide-based etchant or an oxhene etchant is mainly used.

Korean Patent Publication No. 2010-0040352 discloses a hydrogen peroxide type etching solution containing hydrogen peroxide, phosphoric acid, phosphate, chelating agent and cyclic amine compound. However, such a hydrogen peroxide etching solution is disadvantageous in that the disproportionation reaction occurs and the composition itself is decomposed or abruptly changed due to aging.

Particularly, the cyclic amine compound binds to the copper ion generated when the copper film is etched. In this case, when chlorine ions are present in the etching solution, there arises a problem that a poorly soluble precipitate is generated when the chloride ion and the above-mentioned bond react.

In addition, the etchant of the Oxhene etchant has a disadvantage in that the etch rate is slow and unstable over time.

Korea Patent Publication No. 2010-0040352

An object of the present invention is to provide an etching solution composition that does not generate precipitates that are hardly soluble even when the composition contains a cyclic amine compound, a copper salt, and a chlorine compound in the hydrogen peroxide type etching solution composition.

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

It is still another object of the present invention to provide a method of manufacturing a thin film transistor using the etchant composition.

1. An etchant composition for a copper film and a titanium film, comprising a persulfate, a chlorine compound, a copper salt, a cyclic amine compound and an electron donor compound.

2. The etchant composition of claim 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 of claim 1, wherein the chlorine compound is at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride.

4. The etchant composition of claim 1, wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate and ammonium copper phosphate.

5. The method of claim 1, wherein the cyclic amine compound is selected from the group consisting of a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole based compound, a purine based compound, a pyrazole based compound, a pyridine based compound, a pyrimidine based compound, And at least one selected from the group consisting of a fluorine-based compound, a pyrrolidine-based compound, and a pyrroline-based compound.

6. The method of claim 1, wherein the electron donor compound is selected from the group consisting of Glutamic acid, Abietic acid, Metanilic acid, Riboflavin, Folic acid, Gallic acid, and potassium salts, sodium salts, and ammonium salts thereof; And L-isoleucine, adipic acid, palmitic acid, maleic acid, diethylenetriamine pentaacetic acid, N-Acetyl L- cysteine, and methionine (L-methionine), potassium salt, sodium salt and ammonium salt thereof; ≪ / RTI > wherein at least one of the copper film and the titanium film comprises at least one of the copper film and the titanium film.

7. The composition of claim 1 wherein 0.5 to 20% by weight of persulfate, 0.1 to 5% by weight of a chlorine compound, 0.05 to 3% by weight of a copper salt, 0.5 to 5% by weight of a cyclic amine compound and 0.1 to 5% Wherein the copper film and the titanium film comprise a residual amount of water.

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

9. The fluorine compound as set forth in the above 8, wherein the fluorine compound is at least one selected from the group consisting of fluoric acid, ammonium fluoride, ammonium fluoride, ammonium fluoride, potassium fluoride, potassium fluoride, potassium fluoride, sodium fluoride, sodium fluoride, Lithium, and calcium fluoride. 2. The etchant composition of claim 1, wherein the at least one selected from the group consisting of lithium, lithium, and calcium fluoride.

10. The composition of any one of the above 8, wherein the inorganic acid (salt) comprises at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, boric acid and at least one of potassium salt, sodium salt and ammonium salt thereof. Etchant composition.

11. The composition of claim 8, wherein the organic acid (salt) is selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid Malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosuccinic acid, Sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, at least one selected from the group consisting of potassium salt, sodium salt, and ammonium salt of at least one of the foregoing acids, propenoic acid, iminodiacetic acid, and at least one of them.

12. The method of claim 1, wherein the copper film is a copper single film or a copper film and at least one titanium film containing at least one element selected from the group consisting of copper and aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten, Composition.

13. The etchant composition of claim 1, wherein the titanium film is a titanium sole film, the copper film and the titanium film.

14. The etchant composition of claim 1, wherein the copper film and the titanium film are multilayers in which a copper film and a titanium film are alternately laminated one or more times.

15. A method of forming a pattern of a metal wiring comprising etching a copper film and a titanium film with an etching solution composition according to any one of 1 to 14 above.

16. A method 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, a second amorphous silicon layer, a lower data metal layer, and an upper data metal layer on the gate insulating 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 and a drain electrode including a semiconductor, a resistive contact layer, and a source electrode; (f) forming a protective film on the data line, the drain electrode, and the gate insulating film; And (g) forming a pixel electrode connected to the drain electrode on the protective film, the method comprising the steps of:

Wherein the etching of the step (b) and the etching of the step (e) are carried out with the etching liquid composition of any one of 1 to 14 above.

17. The manufacturing method of an array substrate for a liquid crystal display according to 16 above, wherein the lower gate metal layer or the lower data metal layer is formed of a titanium film, and the upper gate metal layer or the upper data metal layer is formed of a copper film.

18. The method of manufacturing an array substrate for a liquid crystal display device according to 17 above, wherein the upper metal layer and the lower metal layer are etched at a time using the etchant.

The etchant composition of the present invention contains an electron donor compound, so that it is possible to suppress the generation of a poorly soluble precipitate even when the composition contains a cyclic amine compound, a copper salt and a chlorine compound.

In addition, the etchant composition of the present invention can uniformly and batch-etch a multi-metal film composed of a copper film and a titanium film at a high etching rate, thereby simplifying the etching process, improving productivity, and securing excellent etching characteristics.

Accordingly, the etchant composition of the present invention can be usefully used in the manufacture of thin film transistors used in array substrates of liquid crystal displays.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing the evaluation of the presence or absence of precipitates according to Example 5 of the present invention. FIG.
Fig. 2 is a photograph showing the evaluation of the presence or absence of precipitate according to Comparative Example 1 of the present invention. Fig.

The present invention relates to a method for simultaneously etching a multi-metal film composed of a copper film and a titanium film at a high etching rate uniformly while preventing generation of a poorly soluble precipitate by including a persulfate, a chlorine compound, a copper salt, a cyclic amine compound and an electron donor compound A copper film and a titanium film, and a method of manufacturing an array substrate for a liquid crystal display device using the same.

Hereinafter, the present invention will be described in more detail.

The term "copper film and titanium film" in the present invention means a multi-metal film in which a copper film and a titanium film are laminated. Specifically, it includes a double metal film in which a copper film / titanium film is stacked in this order, a titanium film / copper film, and a double metal film in this order. Also, a multi-metal film in which a copper film and a titanium film are alternately stacked in three or more layers such as a ternary metal film of a copper film / titanium film / copper film, a ternary metal film of a titanium film / copper film / titanium film, a copper film / A copper film / a titanium film / a copper film, and the like. At this time, the thickness of the copper film and the titanium film is not particularly limited.

The term "copper film" in the present invention may be a copper single film composed of only copper, and may include aluminum (Al), magnesium (Mg), manganese (Mn), beryllium (Be), hafnium (Hf) Nb), tungsten (W), and vanadium (V).

The "titanium film" in the present invention may be a titanium single film composed of titanium alone.

The persulfate contained in the etchant composition of the present invention is a main component for etching the copper film, and also contributes to the etching of the titanium film. Specific examples thereof include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and potassium persulfate (K ₂ S ₂ O ₈ ) Mix more than one species.

The persulfate may be contained in an amount of 0.5 to 20% by weight, preferably 5 to 18% by weight based on the total amount of the etching liquid composition. In this content range, the copper film is etched at a proper amount and an excellent etching profile can be obtained. If the content is less than 0.5% by weight, the copper film may not be etched or the etching rate may be slowed. If the content is more than 20% by weight, the etching rate may be increased and it may be difficult to control the process, so that the copper film and the titanium film may over-

Chlorine compounds are compounds that can dissociate from water to give chloride ions. The chlorine compound serves to adjust the angle of the taper and the auxiliary oxidant that etches the metal film containing copper or copper. Specific examples thereof include hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride, which may be used alone or in admixture of two or more.

The chlorine compound may be contained in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total amount of the etching liquid composition. In this content range, the copper film is etched at a proper amount and an excellent etching profile can be obtained. If the content is less than 0.1% by weight, the etching rate of the copper film may be lowered and the etching profile may be deteriorated. If the content is more than 5% by weight, excessive corrosion may occur and the metal wiring may be lost.

Copper salts serve to regulate CD skew. Specific examples thereof include copper nitrate (Cu (NO ₃ ) ₂ ), copper sulfate (CuSO ₄ ), ammonium copper phosphate (NH ₄ CuPO ₄ ) and the like (excluding persulfates) .

The copper salt may be contained in an amount of 0.05 to 3% by weight, preferably 0.1 to 2% by weight based on the total weight of the etchant composition. A very constant CD skew can be obtained in this content range. If the content is less than 0.05% by weight, variations in the CD skew may vary significantly depending on the number of treatments. If the content is more than 3% by weight, the oxidizing power of the main oxidant may be decreased and the number of treatments may be decreased.

The cyclic amine compound controls the etch rate and reduces the CD loss of the pattern, thereby enhancing the process margin.

Such a cyclic amine compound can be used without any particular limitation as long as it is used in the art. For example, an azole compound having 1 to 30 carbon atoms. More specific examples include a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole-based compound, a purine-based compound, a pyrazole-based compound, a pyridine-based compound, a pyrimidine-based compound, a pyrrole- And the like may be used alone or in combination of two or more.

As the triazole-based compound, for example, compounds represented by the following formula (1) may be used alone or in combination of two or more.

[Chemical Formula 1]

(Wherein R ¹ and R ² are independently of each other a hydrogen atom, a carboxyl group, an amino group, a hydroxy group, a cyano group, a formyl group, a sulfo group, a carboxyl group, an amino group, a hydroxy group, a cyano group, An alkyl or sulfonylalkyl group having 1 to 20 carbon atoms, which may contain an ester group,

Q is a hydrogen atom; A hydroxy group; A substituent represented by the following formula (2); An aryl group having 6 to 20 carbon atoms or an alkyl or alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group and may include at least one of an amide group and an ester group)

(2)

(Wherein R ³ is an alkylene group having 1 to 6 carbon atoms;

R ⁴ and R ⁵ are independently of each other a hydrogen atom, a hydroxy group, or an alkyl, hydroxyalkyl or alkoxyalkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group.

Examples of the compound represented by Formula 1 include 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1- (2,2-dihydroxyethyl) benzotriazole, 1 (1, 2-dihydroxypropyl) benzotriazole, 1- (2,3-dihydroxypropyl) benzotriazole, N, N (2-ethylhexyl) -arylmethyl-1H-benzotriazole-1-methanamine {N, N-BIS- (2-ETHYLHEXYL) -ARYLMETHYL-1H-BENZOTRIAZOLE-1-METHANAMINE} Benzo [b] thiazol-1-yl) methyl] imino} bisethanol and 2,2 '- {[(5-methyl- ] Imino} bisethanol, 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, 5-carboxybenzotriazole dodecyl ester, and the like. These may be used alone or in combination of two or more.

The present invention may further include a triazole-based compound commonly used in the art in addition to the compound represented by the formula (1), for example, 1,2,3-triazole, 1,2,4-triazole, Triazole, 4-amino-1,2,4-triazole, and the like. These may be used alone or in combination of two or more.

Examples of the aminotetrazole compound include aminotetrazole, 5-aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino- Aminotetrazole, 5-aminotetrazole, 1,5-diaminotetrazole, and the like, preferably aminotetrazole.

Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propimidazole, 2-aminoimidazole, , And 4-propylimidazole may be used alone or in combination of two or more.

As the indole-based compound, aminoalkylindole, benzoylindole, methylindole, phenylacetylindole, indolecarbazole, etc. may be used alone or in combination of two or more.

Examples of the purine compound include 6-dimethylaminopurine, 2,6-dichloro-7-methyl-7H-purine, 6- (?,? -Dimethylallylamino) 9-acetic acid and the like can be used singly or in combination of two or more.

Examples of the pyrazole-based compound include 3-phenyl-1H-pyrazole, 3- (aminomethyl) pyrazole, 5- (2-cyanyl) pyrazole, 1- Pyrazole, 5-methyl-1H-pyrazole, 4-nitro-1H-pyrazole, 1H-pyrazole-5-boronic acid, They may be used alone or in combination of two or more.

Examples of the pyridine compound include 4- (aminoethyl) pyridine, 2- (methylamino) pyridine, pyridine trifluoroacetate, pyridine- -Benzoic acid may be used alone or in combination of two or more.

As the pyrimidine-based compound, pyrimidine-5-carboxylic acid, pyrimidine-2-carboxylic acid, etc. may be used each alone or in combination of two or more.

Examples of the pyrrole compound include pyrrole-2-carboxylic acid, pyrrole-3-carboxylic acid, 1- (2-aminophenyl) pyrrole, Can be used.

Examples of the pyrrolidine-based compound include 1- (2-aminoethyl) pyrrolidine, pyrrolidine-3-carboxylic acid, pyrrolidine-3-carboxylic acid hydrochloride, pyrrolidine- 2-dicarboxylic acid 1-phenyl ester, and the like, or a mixture of two or more thereof.

As the pyrroline compound, 3-pyrroline, 2-methyl-1-pyrroline, 1-benzyl-3-pyrroline and the like may be used either singly or as a mixture of two or more thereof.

The total content of the cyclic amine compound may be 0.5 to 5 wt%, preferably 1 to 4 wt%, based on the total weight of the etchant composition. It is possible to maintain an appropriate etching rate within the above range and to exhibit excellent etching characteristics. If the content is less than 0.5% by weight, the etching rate of copper can not be controlled and an excessive angle may occur. If the content exceeds 5% by weight, the etching time of the copper-based metal film may become too slow, .

The electron donor compound prevents precipitation of insoluble precipitates by bonding a positive charge region of copper ions chelating with the cyclic amine compound to a chloride ion derived from a chlorine compound. Specifically, electrons are supplied to the positive charge region to prevent the bonding of chlorine ions.

The electron donor compound may use at least one of a cyclic organic compound and a non-cyclic organic compound.

The cyclic organic compound may be selected from the group consisting of glutamic acid, abietic acid, methanilic acid, riboflavin, Folic acid, Gallic acid and ascorbic acid. And at least one salt compound selected from the group consisting of potassium salt, sodium salt and ammonium salt of at least one compound selected from the group consisting of Ascorbic acid, and a compound selected therefrom. Representative salt compounds include potassium L-ascorbate, calcium L-ascorbate, and sodium L-ascorbate.

The non-cyclic organic compound is selected from the group consisting of L-isoleucine, adipic acid, palmitic acid, maleic acid, diethylenetriamine pentaacetic acid, acetylcysteine (N -Acetyl L-cysteine) and methionine (L-methionine), or a compound selected from the group consisting of potassium salt, sodium salt and ammonium salt thereof.

More preferred examples of the electron donor compound include riboflavin, folic acid, gallic acid, ascorbic acid, diethylenetriamine pentaacetic acid, acetylcysteine Which consists of N-acetyl L-cysteine, L-methionine, Potassium L-ascorbate, Calcium L-ascorbate and Sodium L-ascorbate At least one selected from the group consisting of

The electron donor compound may be contained in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight based on the total weight of the etchant composition. If the content is less than 0.1% by weight, the possibility of generating a poorly soluble precipitate may be high, and if it exceeds 5% by weight, the etching performance of the etching composition may be deteriorated.

If necessary, the etchant composition of the present invention may further comprise at least one selected from the group consisting of fluorine compounds, inorganic acids (salts) and organic acids (salts).

The fluorine compound means a compound capable of releasing fluorine ions from water. The fluorine-containing compound is a component that etches the titanium film and serves to remove residues from the titanium film.

Specific examples of the fluorine compound include fluorine compounds such as fluoric acid, ammonium fluoride, ammonium fluoride, ammonium fluoride, potassium fluoride, potassium fluoride, potassium fluoride, sodium fluoride, sodium fluoride, fluoride, boron fluoride, These may be used alone or in combination of two or more.

The fluorine-containing compound may be contained in an amount of 0.01 to 2% by weight, preferably 0.1 to 1% by weight based on the total amount of the composition. Within this range, the etching power and the residue-restraining force are the most excellent. If the content is less than 0.01% by weight, etch residue may be generated. If the content is more than 2.0% by weight, the etching rate of other layers such as a substrate may be increased.

In the present invention, the inorganic acid (salt) refers to an inorganic acid, a salt of an inorganic acid, or both. The inorganic acid (salt) is a co-oxidant for the etching of the copper film and the titanium film, and the etching rate can be controlled according to the content in the etching solution composition of the inorganic acid (salt). In addition, the inorganic acid (salt) can react with copper ions in the etchant composition, thereby preventing the increase of the copper ion and preventing the etching rate from decreasing.

Specific examples of the inorganic acid (salt) include at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, boric acid and perchloric acid and salts thereof, and examples of the salt include potassium salt, sodium salt and ammonium salt . These may be used alone or in combination of two or more.

The inorganic acid (salt) may be 1 to 10% by weight, preferably 2 to 7% by weight based on the total amount of the etching liquid composition. In this range, the copper film and the titanium film can be etched in an appropriate amount and have an excellent etching profile. If the content is less than 1% by weight, the etching rate may be lowered and the etching profile may become poor and residues may be generated. If the content is more than 10% by weight, an excessive angle may occur, cracks may occur in the photoresist, The etching solution composition may penetrate and the copper film or the titanium film located under the etching composition may be excessively etched.

In the present invention, the organic acid (salt) refers to an organic acid, a salt of an organic acid, or both. The organic acid (salt) is adsorbed on the surface of the copper film and the titanium film to improve the etching uniformity and to maintain a constant etching profile in the progress of the number of treatments in order to obtain a desired side etching. The organic acid salt acts as a chelate to form a complex with the copper ion in the etchant composition, thereby controlling the etching rate of copper. As a result, the number of treatments increases .

Specific examples of the organic acid (salt) include acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, malonic acid, oxalic acid, pentanoic 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, propenoic acid, at least one selected from the group consisting of propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid (EDTA) and salts thereof, and the salts include potassium salt, sodium salt and Ammonium salts are examples. These may be used alone or in combination of two or more.

The organic acid (salt) may be 0.1 to 10% by weight, preferably 1 to 8% by weight based on the total amount of the etching liquid composition. In this range, the copper film and the titanium film can be etched in an appropriate amount and have an excellent etching profile. If the content is less than 0.1% by weight, the etching rate may be lowered and the etching profile may become poor and residues may be generated. If the content is more than 10% by weight, excessive etching may occur, The increasing effect may not be exerted anymore.

In the etchant composition of the present invention, water is contained in the remaining amount other than the content of the other components such that the total weight of the composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. It is more preferable to use deionized water having a water resistivity value of 18 M? 占 cm m or more, which shows the degree of removal of ions in water.

In the etchant composition of the present invention, conventional additives may be further added in addition to the above-mentioned components. Examples of the additive include, but are not limited to, an etch control agent, a metal ion sequestrant, a corrosion inhibitor, a surfactant, and a pH adjuster.

In the etchant composition of the present invention thus constructed, not only a double metal film in which a copper film and a titanium film are stacked but also a multi-metal film in which they are stacked two or more times are uniformly etched uniformly at a high etching rate and at the same time insoluble precipitates are not generated. Through this, the etching process can be simplified, productivity can be improved, and excellent etching characteristics can be secured.

The present invention also provides a method of forming a pattern of a metal wiring by etching a copper film and a titanium film with the etching solution composition of the present invention. Such a metal wiring forming method can be usefully used for forming a thin film transistor array substrate. Such a thin film transistor array substrate can also be used for manufacturing an array substrate for a liquid crystal display, a memory semiconductor substrate, and the like.

Accordingly, the present invention provides a method of manufacturing an array substrate for a liquid crystal display using the above-mentioned etchant composition. Specifically, when a copper film and a titanium film are used as a gate line or a data line and a drain electrode, they can be used for etching for manufacturing.

One embodiment of a method of manufacturing an array substrate for a liquid crystal display according to the present invention includes 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 silicon layer, a second amorphous silicon layer, a lower data metal layer, and an upper data metal layer on the gate insulating 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 and a drain electrode including a semiconductor, a resistive contact layer, and a source electrode;

(f) forming a protective film on the data line, the drain electrode, and the gate insulating film; And

(g) forming a pixel electrode connected to the drain electrode on the protective film, the method comprising the steps of:

The etching of the step (b) and the etching of the step (e) may be performed with the etching composition of the present invention.

As a preferred example, the lower gate metal layer or the lower data metal layer may be formed of a titanium film, and the upper gate metal layer or the upper data metal layer may be formed of a copper film. In this case, It is possible to etch the substrate at a time using the etching liquid, so that the array substrate can be manufactured more simply.

For reference, the specific contents of the manufacturing method of the array substrate for a liquid crystal display device are all disclosed in Korean Patent Publication No. 2012-0111636.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example

An etchant composition was prepared (unit weight%) according to the composition shown in Table 1 below.

SPS ABF HNO ₃ ATZ NaCl CuSO ₄ AcOH Electron donation
compound Kinds content Example 1 10 0.5 3 1.5 1.5 0.2 3 A-1 0.3 Example 2 10 0.5 3 1.5 1.5 0.2 3 A-2 3 Example 3 10 0.5 3 1.5 1.5 0.2 3 A-3 0.3 Example 4 10 0.5 3 1.5 1.5 0.2 3 A-4 3 Example 5 10 0.5 3 1.5 1.5 0.2 3 A-5 3 Example 6 10 0.5 3 1.5 1.5 0.2 3 A-6 3 Example 7 10 0.5 3 1.5 1.5 0.2 3 A-7 3 Example 8 10 0.5 3 1.5 1.5 0.2 3 A-8 3 Example 9 10 0.5 3 1.5 1.5 0.2 3 A-9 0.1 Example 10 10 0.5 3 1.5 1.5 0.2 3 A-10 2 Comparative Example 1 10 0.5 3 1.5 1.5 0.2 3 - - SPS: Sodium persulfate
ABF: Ammonium bifluoride
ATZ: 5-aminotetrazole
AcOH: Acetic acid
A-1: Riboflavin
A-2: Folic acid
A-3: Gallic acid
A-4: Ascorbic acid
A-5: Potassium L-ascorbate7
A-6: Calcium L-ascorbate
A-7: Sodium L-ascorbate
A-8: Diethylenetriamine pentaacetic acid
A-9: N-Acetyl L-cysteine
A-10: L-Methionine

Test Example

One. Precipitate  Assessment of occurrence

Evaluation was made as to whether the precipitates were generated as described below for the etching solutions according to Examples 1 to 11 and Comparative Example 1 of the present invention.

Add Cu 3000 ppm Powder to the prepared etch solution and completely dissolve for 30 minutes using Stirrer. The resultant was placed in a prepared PE bottle and kept at a low temperature (-9 ° C or less) under severe conditions. The presence or absence of precipitation was observed in real time, and the results are shown in Table 2.

2. Etching  Performance evaluation

The etching characteristics of the etching solutions according to Examples 1 to 11 and Comparative Example 1 of the present invention were evaluated as follows.

A SiNx layer is deposited on the glass, a titanium film is deposited on the SiNx layer, and a copper film is deposited on the titanium film. On the copper film, a substrate patterned with a photoresist pattern having a predetermined shape was cut out with a diamond knife to a size of 550 × 650 mm.

The etching solutions of Examples 1 to 11 and Comparative Example 1 were placed in an experimental apparatus of a spray-type etching system and the temperature was raised to 25 占 폚. Thereafter, after the temperature reached 30 +/- 0.1 DEG C, the etching process was performed. Total etch time was 200% over etch based on EPD. When the etching was completed, the specimen was injected. After the etching was completed, the substrate was rinsed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist stripper. After cleaning and drying, the etching characteristics were evaluated using a scanning electron microscope.

-9 ℃ Storage
Observation of precipitation Etching performance 1 day 7 days 15th Example 1 none none none Good Example 2 none none none Good Example 3 none none none Good Example 4 none none none Good Example 5 none none none Good Example 6 none none none Good Example 7 none none none Good Example 8 none none none Good Example 9 none none none Good Example 10 none none none Good Comparative Example 1 Occur increase increase Good

Referring to Table 2, it can be confirmed that precipitates did not occur in all of the etching solutions of Examples, but precipitates occurred in Comparative Example 1. For reference, Fig. 1 shows the photograph of the precipitate evaluation of Example 5, and Fig. 2 shows the evaluation photograph of Comparative Example 1. Fig.

In addition, it is understood that even if an electron donor compound is further added, the etching property is not deteriorated.

Claims (18)

A copper and titanium film etchant composition comprising a persulfate, a chlorine compound, a copper salt, a cyclic amine compound, and an electron donor compound.
The etchant composition of 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 of claim 1, wherein the chlorine compound is at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride.
The etchant composition of claim 1, wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate and ammonium copper phosphate.
[3] The method according to claim 1, wherein the cyclic amine compound is at least one selected from the group consisting of a triazole-based compound, an aminotetrazole-based compound, an imidazole-based compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, A pyrrolidine-based compound, and a pyrroline-based compound.
2. The electron donor compound according to claim 1,
The present invention relates to a method for producing a compound of formula (I) or a salt thereof, wherein the compound is selected from the group consisting of glutamic acid, abietic acid, methanilic acid, riboflavin, folic acid, gallic acid, At least one selected from the group consisting of ammonium salts; And
But are not limited to, L-isoleucine, adipic acid, palmitic acid, maleic acid, diethylenetriamine pentaacetic acid, N-Acetyl L-cysteine ), And methionine (L-methionine); at least one selected from the group consisting of potassium salts, sodium salts and ammonium salts thereof; ≪ / RTI > wherein at least one of the copper film and the titanium film comprises at least one of the copper film and the titanium film.
The method according to claim 1, wherein the amount of the persulfate is from 0.5 to 20% by weight, the chlorine compound is from 0.1 to 5% by weight, the copper salt is from 0.05 to 3% by weight, the cyclic amine compound is from 0.5 to 5% The etching solution composition of a copper film and a titanium film comprising water.
The etchant composition of claim 1, further comprising at least one selected from the group consisting of a fluorine compound, an inorganic acid (salt) and an organic acid (salt).
The method of claim 8, wherein the fluorine compound is selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium fluoride, ammonium fluoride, potassium fluoride, potassium bisulfide, potassium fluoroborate, sodium fluoride, sodium bisulfite, aluminum fluoride, And at least one selected from the group consisting of calcium fluoride and calcium fluoride.
9. The etchant composition of claim 8, wherein the inorganic acid (salt) comprises at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, boric acid and at least one of potassium, sodium and ammonium salts thereof. .
The method of claim 8, wherein the organic acid (salt) is selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, But are not limited to, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, At least one selected from the group consisting of potassium salt, sodium salt, and ammonium salt of at least one of them, propenoic acid, iminodiacetic acid, and the like.
The etchant composition of claim 1, wherein the copper film comprises at least one selected from the group consisting of copper alone or copper and aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten, and vanadium.
The etchant composition of claim 1, wherein the titanium film is a titanium sole film.
The etchant composition of claim 1, wherein the copper film and the titanium film are multilayers in which a copper film and a titanium film are alternately laminated one or more times.
A method for forming a pattern of a metal wiring comprising etching a copper film and a titanium film with the etching solution composition according to any one of claims 1 to 14.
(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, a second amorphous silicon layer, a lower data metal layer, and an upper data metal layer on the gate insulating 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 and a drain electrode including a semiconductor, a resistive contact layer, and a source electrode;
(f) forming a protective film on the data line, the drain electrode, and the gate insulating film; And
(g) forming a pixel electrode connected to the drain electrode on the protective film, the method comprising the steps of:
Wherein the etching of the step (b) and the etching of the step (e) are performed with the etching liquid composition of any one of claims 1 to 14.
17. The method of claim 16, wherein the lower gate metal layer or the lower data metal layer is formed of a titanium film, and the upper gate metal layer or the upper data metal layer is formed of a copper film.
18. The method of claim 17, wherein the upper metal layer and the lower metal layer are etched at a time using the etchant.

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