KR20170011828A - Etchant composition and manufacturing method of an array substrate for liquid crystal display - Google Patents

Abstract

The present invention relates to an etchant composition, and a method for manufacturing an array substrate for a liquid crystal display device. According to the present invention, an etching profile is excellent and the number of processed films is large when a copper-based metal film is etched by the etchant composition. The preset invention comprises: a step of forming gate wiring; a step of forming a gate insulation layer; a step of forming a semiconductor layer; a step of forming source and drain electrodes; and a step of forming a pixel electrode.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching liquid composition for a liquid crystal display device,

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

A typical example of an electronic circuit for driving a semiconductor device and a flat panel display device is a thin film transistor (TFT). The manufacturing process of the TFT is generally composed of forming a metal film as a gate and a data wiring material on a substrate, forming a photoresist in a selective region of the metal film, and etching the upper metal film using the photoresist as a mask.

The gate wiring and the data wiring use a copper having a good electrical conductivity and a low resistance, and in the case of copper, there is a difficulty in the process of applying and patterning the photoresist. In recent years, Based metal film. Among the copper-based metal films, titanium / copper double films are generally used. However, when the titanium / copper double layer is etched at the same time, the etching profile is poor and the subsequent process is difficult, and there is a disadvantage that the copper to be eluted as the etching proceeds and the number of the processed layers are accordingly low. As a result, Korean Patent Laid-Open Publication No. 2015-0059800 provides a liquid composition containing a maleic acid ion source, a copper ion source and a fluoride ion source and having a pH value of 0 to 7 have. However, the liquid composition has a disadvantage that the etching profile is poor and the ability of the number of sheets to be processed is poor.

Therefore, there is a continuing need for research on etchant compositions having an excellent etch profile and a high number of treatments when etching a copper-based metal film such as a titanium / copper double film.

Korea Patent Publication No. 2015-0059800

Accordingly, it is an object of the present invention to provide a copper-based metal film etchant composition having an excellent etching profile and a high number of treatments.

In order to solve the above problems,

0.5 to 10% by weight of a copper compound;

0.01 to 2% by weight of a fluorine compound;

1 to 10% by weight of at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid;

At least one chlorine compound selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride 0.1 to 10 wt. %;

There may be mentioned 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, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, 1 to 10% by weight of at least one organic acid or salt thereof selected from the group consisting of tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid;

At least one nonmetal inorganic salt selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, 0.1 to 10% by weight;

0.01 to 5% by weight of a cyclic amine compound;

0.5 to 10% by weight of a chelating agent; And

Water balance,

The chelating agent may be selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, 5-norbornene-exo-2,3-dicarboxylic acid (cis -5-norbornene-exo- 2,3-dicarboxylic acid), 1,2,3,4- cyclo butane tetracarboxylic acid (1, 2, 3 , 4-cyclobutanetetracarboxylic acid) and cis, cis, cis, -1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, Cis-1,2,3,4-cyclopentanetetracarboxylic acid) And the copper-based metal film etchant composition is at least one selected from the group consisting of the copper-based metal film etchant composition or the salt thereof.

In one embodiment, the copper-based metal film may be titanium or a titanium alloy and a copper or copper alloy double film.

The present invention also provides a method of manufacturing a semiconductor device, comprising the steps of: a) forming a gate wiring on a substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming a semiconductor semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

The step a) or the step d) includes forming a copper-based metal film on the substrate or the semiconductor layer, and etching the copper-based metal film with the etchant composition to form a gate wiring or a source and a drain electrode,

The etchant composition comprises, based on the total weight of the composition, 0.5 to 10% by weight of a copper compound; 0.01 to 2% by weight of a fluorine compound; 1 to 10% by weight of at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid; At least one chlorine compound selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride 0.1 to 10 wt. %; There may be mentioned 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, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, 1 to 10% by weight of at least one organic acid or salt thereof selected from the group consisting of tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid; At least one nonmetal inorganic salt selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, 0.1 to 10% by weight; 0.01 to 5% by weight of a cyclic amine compound; Maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, melitic acid, 4-sulfophthalic acid, quinolanic acid, cis-5-norbornene Cis- 5-norbornene-exo-2,3-dicarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid (1,2,3,4-cyclobutanetetracarboxylic acid ) And cis, cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, Cis-1,2,3,4-cyclopentanetetracarboxylic acid) From 0.5 to 10% by weight of a chelating agent which is at least one or a salt thereof; And a remaining amount of water. The present invention also provides a method of manufacturing an array substrate for a liquid crystal display.

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

In another embodiment, the copper-based metal film may be titanium or a titanium alloy and a copper or copper alloy double film.

The present invention also provides an array substrate for a liquid crystal display manufactured by the above manufacturing method.

When the copper-based metal film is etched with the etchant composition of the present invention, it has an excellent etching profile and a high number of treatments.

Fig. 1 shows the profiles of the etchant compositions of Example 1 and Comparative Example 11 at the time of etching the titanium / copper double layer.

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

DETAILED DESCRIPTION OF THE INVENTION The etchant composition of the present invention comprises, as a chelating agent, maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, , quinolyl nolsan, cis-5-norbornene-exo-2,3-dicarboxylic acid (cis -5-norbornene-exo- 2,3-dicarboxylic acid), 1,2,3,4- cyclo butane tetracarboxylic acid ( 1,2,3,4-cyclobutanetetracarboxylic acid) and cis, cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, -cyclopentanetetracarboxylic acid) or a salt thereof, the etching profile is excellent and the number of treatments is high when the copper-based metal film is etched.

Hereinafter, the present invention will be described in detail.

Etchant  Composition

In the present invention, the copper compound serves to oxidize and maintain the CD skew unchanged when the etchant is etched, and the copper compound is contained in an amount of 0.5 to 10% by weight based on the total weight of the etchant desirable. If the content is less than 0.5% by weight, the metal film including copper or copper is not etched or the etching rate is very slow and the initial etching is not uniform. If it is more than 10% by weight, the effect of increasing the number of treatments is not obtained. The copper compound is preferably at least one selected from the group consisting of copper sulfate, copper chloride and copper nitrate.

The fluorine compound is a main component that etches a metal film including titanium or titanium, and removes residues that may be formed during etching. The fluorine compound is preferably contained in an amount of 0.01 to 2% by weight based on the total weight of the etching solution. If the content of the fluorine compound is less than 0.01% by weight, the etching rate of the metal film containing titanium or titanium may be lowered to cause residue, and if it exceeds 2.0% by weight, It may cause damage to the insulating film including silicon formed together. The fluorine compound may be a compound in which a fluorine ion or a polyatomic fluorine ion is dissociated in a solution. Examples of the fluorine compound include ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride ), Sodium bifluoride, and potassium bifluoride are preferably used.

At least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid is a co-oxidant for etching a metal film comprising copper or copper and a metal film comprising titanium or titanium, By weight to 10% by weight. If the content of the inorganic acid is less than 1% by weight, the etching rate of the metal film including copper or copper and the metal film including titanium or titanium may be lowered, resulting in poor etching profile and residue, , Overexcitation angles and photoresist cracks may occur, and the wiring may be short-circuited by the penetration of the chemical liquid.

At least one chlorine compound selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride, The role of oxidant, the etching speed and the angle of the metal film are controlled, and the wiring can be prevented from being opened. The chlorine compound is preferably contained in an amount of 0.1 to 10% by weight based on the total weight of the composition. If the content of the chlorine compound is less than 0.1% by weight, the etching rate of copper may be lowered and the etching time may be prolonged in the process, resulting in a problem in productivity. In addition, if it exceeds 10% by weight, the etching rate of copper can not be controlled, and an overeating angle may occur.

There may be mentioned 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, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, , At least one organic acid or salt thereof selected from the group consisting of tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid may increase the solubility and lower the pH of the copper ion and the chelating agent, It serves to control the etching rate. The organic acid or its salt is preferably contained in an amount of 1 to 10% by weight based on the total weight of the etching solution. If the content of the organic acid or the organic acid salt is less than 1% by weight, the effect of increasing the number of treatments is not obtained. If the content is more than 10% by weight, overcorrection may occur and the wiring may be short-circuited.

At least one nonmetal inorganic salt selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, Serves as an auxiliary etching control agent for the metal film and has an effect of improving the poor etching profile which is a disadvantage of the etching solution containing the chlorine compound. The non-metallic inorganic salt is preferably contained in an amount of 0.1 to 10% by weight based on the total weight of the composition. If it is less than 0.1% by weight, it does not have an effect of improving the auxiliary etching control agent and improving the etching profile, and if it exceeds 10% by weight, overeating angle may occur.

The cyclic amine compound is a batch etching and angle-adjusting etching control agent including copper or copper. The cyclic amine compound is preferably contained in an amount of 0.01 to 5% by weight based on the total weight of the composition. If it is less than 0.01% by weight, uniform etching of the metal film is not achieved, and if it exceeds 5% by weight, the etching rate may be lowered. The cyclic amine compound may be selected from the group consisting of 5-aminotetrazole, triazole, phenyltetrazole, imidazole, indole, purine, pyrazole, pyridine, It is preferable to use at least one member selected from the group consisting of pyrimidine, pyrrole, pyrrolidine, pyrroline and 5-methyltetrazole.

Water means deionized water and is used for semiconductor processing, and preferably water of 18 M / cm or more is used. With respect to the total amount of the etchant, water is contained in such an amount that the total weight of the etchant is 100% by weight.

Maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, melitic acid, 4-sulfophthalic acid, quinolanic acid, cis-5-norbornene Cis- 5-norbornene-exo-2,3-dicarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid (1,2,3,4-cyclobutanetetracarboxylic acid ) And cis, cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, Cis-1,2,3,4-cyclopentanetetracarboxylic acid) The chelating agent which is at least one kind or a salt thereof acts as a main component for increasing the number of treatments and is preferably contained in an amount of 0.5 to 10% by weight based on the total weight of the composition. If the amount is less than 0.5% by weight, the effect of increasing the number of treatments is not exhibited. If the amount is more than 10% by weight, the etching rate of the metal film may increase and an overeating angle may occur.

In the present invention, the etchant composition may further include a sequestering agent, a corrosion inhibitor, and the like.

Method for manufacturing array substrate for liquid crystal display

In the method for manufacturing an array substrate for a liquid crystal display of the present invention,

a) forming a gate wiring on the substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming a semiconductor semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

The steps a) and d) include forming a copper-based metal film on the substrate or the semiconductor layer, and etching the copper-based metal film with the etchant composition of the present invention to form a gate wiring or a source and a drain electrode And a method of manufacturing a liquid crystal display array substrate.

The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate, but is not limited thereto and may be used for manufacturing other electronic devices including a metal wiring made of a copper-based metal film such as a memory semiconductor substrate.

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

Example  1 to 15 and Comparative Example  1 to 15. Etchant  Preparation of composition

The composition of the etchant was prepared according to the composition and the content (unit: wt%) shown in Table 1 below.

division (A) (B) (C) (D) (E) (F) (G) (H) (I) water Example 1 3 0.5 5 6 2 3 One 2 - Balance Example 2 0.5 0.5 5 6 2 3 One 2 - Balance Example 3 10 0.5 5 6 2 3 One 2 - Balance Example 4 3 0.5 One 6 2 3 One 2 - Balance Example 5 3 0.5 10 6 2 3 One 2 - Balance Example 6 3 0.5 5 One 2 3 One 2 - Balance Example 7 3 0.5 5 10 2 3 One 2 - Balance Example 8 3 0.5 5 6 0.3 3 One 2 - Balance Example 9 3 0.5 5 6 10 3 One 2 - Balance Example 10 3 0.5 5 6 2 One One 2 - Balance Example 11 3 0.5 5 6 2 10 One 2 - Balance Example 12 3 0.5 5 6 2 3 0.05 2 - Balance Example 13 3 0.5 5 6 2 3 5 2 - Balance Example 14 3 0.5 5 6 2 3 One One - Balance Example 15 3 0.5 5 6 2 3 One 10 - Balance Comparative Example 1 3 0.5 5 6 2 3 One - - Balance Comparative Example 2 3 0.5 5 6 2 3 One - 2 Balance Comparative Example 3 - 0.5 5 6 2 3 One 2 - Balance Comparative Example 4 13 0.5 5 6 2 3 One 2 - Balance Comparative Example 5 3 0.5 0.5 6 2 3 One 2 - Balance Comparative Example 6 3 0.5 13 6 2 3 One 2 - Balance Comparative Example 7 3 0.5 5 - 2 3 One 2 - Balance Comparative Example 8 3 0.5 5 13 2 3 One_ 2 - Balance Comparative Example 9 3 0.5 5 6 0 3 One 2 - Balance Comparative Example 10 3 0.5 5 6 13 3 One 2 - Balance Comparative Example 11 3 0.5 5 6 2 0 One 2 - Balance Comparative Example 12 3 0.5 5 6 2 13 One 2 - Balance Comparative Example 13 3 0.5 5 6 2 3 0 2 - Balance Comparative Example 14 3 0.5 5 6 2 3 7 2 - Balance Comparative Example 15 3 0.5 5 6 2 3 One 13 - Balance

(A): Cu (II) SO ₄

(B): Ammonium fluoride

(C): nitric acid

(D): Citric acid

(E): Ammonium chloride

(F): Ammonium sulfate

(G): 5-methyl tetrazole

(H): Phthalic acid

phthalic acid (benzene-1,2-dicarboxylic acid)

(I): Terephthalic acid

terephthalic acid (benzene-1,4-dicarboxylic acid)

Experimental Example . Etching  Character rating

The etching compositions of Examples 1 to 15 and Comparative Examples 1 to 15 were used to carry out the etching process. (ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 30 캜 in the etching process. The etching time may be different depending on the etching temperature, but it is usually 30 to 80 seconds in the LCD etching process. The profile of the etched titanium / copper double-layer film in the etching process was observed using SEM (Hitachi, Model S-4700). The results are shown in Table 2 and FIG.

division Number of processing
(ppm) Example 1 6000 Example 2 5500 Example 3 6500 Example 4 5000 Example 5 7000 Example 6 5000 Example 7 7000 Example 8 5000 Example 9 7000 Example 10 5500 Example 11 6500 Example 12 6000 Example 13 6500 Example 14 5000 Example 15 10000 Comparative Example 1 4000 Comparative Example 2 4000 Comparative Example 3 Un-Etch Comparative Example 4 5500 Comparative Example 5 Etch rate degradation Comparative Example 6 Overeating angle Comparative Example 7 3000 Comparative Example 8 Overeating angle Comparative Example 9 Etch rate degradation Comparative Example 10 Overeating angle Comparative Example 11 Degradation of etch rate / Bad etching profile Comparative Example 12 Overeating angle Comparative Example 13 Non-uniform etching Comparative Example 14 Etch rate degradation Comparative Example 15 Overeating angle

Un-Etch: Non-patterned Cu is not etched and no pattern is formed

Etching profile defect: When SEM measurement, it indicates the straightness of the Cu part of the pattern part and the defect of the slope.

As shown in Table 2, Examples 1 to 15 are superior to Comparative Examples 1 to 15 in terms of the number of processes and etching profile. In particular, as shown in Figure 1, Example 1 exhibited an excellent etch profile as compared to Comparative Example 11 where no inorganic salt (ammonium sulfate) was added.

Claims (7)

With respect to the total weight of the composition,
0.5 to 10% by weight of a copper compound;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid;
At least one chlorine compound selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride 0.1 to 10 wt. %;
There may be mentioned 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, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, 1 to 10% by weight of at least one organic acid or salt thereof selected from the group consisting of tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid;
At least one nonmetal inorganic salt selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, 0.1 to 10% by weight;
0.01 to 5% by weight of a cyclic amine compound;
0.5 to 10% by weight of a chelating agent; And
Water balance,
The chelating agent may be selected from the group consisting of maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, mellitic acid, 4-sulfophthalic acid, 5-norbornene-exo-2,3-dicarboxylic acid (cis -5-norbornene-exo- 2,3-dicarboxylic acid), 1,2,3,4- cyclo butane tetracarboxylic acid (1, 2, 3 , 4-cyclobutanetetracarboxylic acid) and cis, cis, cis, -1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, Cis-1,2,3,4-cyclopentanetetracarboxylic acid) Wherein the copper-based metal film etchant composition is at least one selected from the group consisting of the copper-based metal film etchant composition and the copper-based metal film etchant composition. The method according to claim 1,
Wherein the copper-based metal film is titanium or a titanium alloy and a copper or copper alloy double film. a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The step a) or the step d) includes forming a copper-based metal film on the substrate or the semiconductor layer, and etching the copper-based metal film with the etchant composition to form a gate wiring or a source and a drain electrode,
The etchant composition comprises, based on the total weight of the composition, 0.5 to 10% by weight of a copper compound; 0.01 to 2% by weight of a fluorine compound; 1 to 10% by weight of at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid; At least one chlorine compound selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, methanesulfonyl chloride, ethanesulfonyl chloride, chlorobenzenesulfonyl chloride, benzenesulfonyl chloride and chloroethanesulfonyl chloride 0.1 to 10 wt. %; There may be mentioned 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, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, 1 to 10% by weight of at least one organic acid or salt thereof selected from the group consisting of tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid; At least one nonmetal inorganic salt selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, 0.1 to 10% by weight; 0.01 to 5% by weight of a cyclic amine compound; Maleic acid, citraconic acid, phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, melitic acid, 4-sulfophthalic acid, quinolanic acid, cis-5-norbornene Cis- 5-norbornene-exo-2,3-dicarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid (1,2,3,4-cyclobutanetetracarboxylic acid ) And cis, cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid (Cis, Cis, Cis, Cis-1,2,3,4-cyclopentanetetracarboxylic acid) From 0.5 to 10% by weight of a chelating agent which is at least one or a salt thereof; And a remaining amount of water. ≪ RTI ID = 0.0 > 11. < / RTI > The method of claim 3,
Wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate. The method of claim 3,
Wherein the copper-based metal film is titanium or a titanium alloy and a copper or copper alloy double-layered film. The method of claim 3,
Wherein the copper-based metal film is titanium or a titanium alloy and a copper or copper alloy double-layered film. An array substrate for a liquid crystal display device manufactured by the manufacturing method of claim 3.

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