KR20180066764A - Etching solution composition, etching method using thereof and preparing method of an array substrate for display using the same - Google Patents

Abstract

Provided are a multimembrane etching composition, an etching method using the same, and a method for producing an array substrate for display devices using the same. To this end, the multimembrane etching composition comprises: A) about 0.5-20.0 wt% by weight of persulfate; B) about 0.01-2.0 wt% of a fluorine compound; C) about 5.0-15.0 wt% of inorganic acid; D) about 10.0-30.0 wt% of organic acid; E) about 0.1-10.0 wt% of an organic acid salt; F) about 0.1-5.0 wt% of a cyclic amine compound; G) about 0.1-6.0 wt% of sulfamic acid; H) about 0.1-5.0 wt% of glycine; and I) residual water.

Description

[0001] The present invention relates to a multi-layer etchant composition, an etching method using the multi-layer etchant composition, and a method of manufacturing an array substrate for a display device using the same.

The present invention relates to a multi-film etching liquid composition, an etching method using the same, and a method of manufacturing an array substrate for a display device using the same.

A liquid crystal display device (LCD device) is one of the most popular flat panel display devices because it provides clear images according to excellent resolution, consumes less electricity, and makes a display screen thinner. A typical example of an electronic circuit for driving a display element used in such a liquid crystal display today is a thin film transistor (TFT) circuit, and a typical thin film transistor liquid crystal display (TFT-LCD) element constitutes a pixel of a display screen. TFTs serving as switching elements in TFT-LCD devices are manufactured by filling a liquid crystal material between a TFT container plate arranged in a matrix form and a color filter substrate facing the substrate. The overall manufacturing process of TFT-LCD is divided into TFT substrate manufacturing process, color filter process, cell process, and module process. TFT substrate and color filter manufacturing process are very important in showing accurate and clear images.

In order to realize a line of a desired electric circuit on a pixel display electrode, etching (etching) process of cutting a thin film layer in accordance with a circuit pattern is required.

However, existing etchant compositions can be collectively etched on the bilayers made by depositing the main wiring on the barrier film, but the wet etching process is performed on the wirings deposited on the more various kinds of metal and the more multilayered Is not easy. Specifically, in the case of a quaternary film, the same etching amount should be maintained for all the quaternary films. Since the etching rates of the respective films corresponding to the quaternary films are different from each other, there is a problem that the films are not uniformly etched due to the different etching rates do.

Korean Patent Laid-Open No. 10-2015-0089887 discloses an etchant composition for performing double-layer etching of titanium-copper using persulfate without using hydrogen peroxide as a main oxidizing agent. However, The wet etching process for the multilayer deposited wiring has a problem that the batch etching effect is lowered. To solve this problem, there is a need for an improved etchant composition capable of etching multiple films.

Korean Patent Publication No. 10-2015-0089887

The present invention provides an etchant capable of collectively etching wirings made of various metal types and multiple films for future multifunctional purposes such as multiple films including an indium oxide film used as a pixel electrode of a display device array substrate, It is an object of the present invention to provide a multi-film etching liquid composition for improving the driving characteristics of a thin film transistor-display element capable of reducing the entire process time and cost reduction, an etching method using the same, and a method for manufacturing an array substrate for a display device using the same.

B) from about 0.01% to about 2.0% by weight of a fluorine compound; and from about 0.5% to about 20.0% by weight of a sulfuric acid salt; C) from about 5.0% to about 15.0% by weight of an inorganic acid; D) from about 10.0 to about 30.0% by weight of organic acid; E) from about 0.1% to 10.0% by weight of an organic acid salt; F) from about 0.1% to about 5.0% by weight of a cyclic amine compound;

G) from about 0.1% to about 6.0% by weight of sulfamic acid; H) glycine about 0.1 wt% to about 5.0 wt%; And I) balance water. ≪ Desc / Clms Page number 5 >

(1) forming a multi-layer on a substrate; (2) selectively leaving a photoreactive material on the multiple layers; And (3) etching the multi-layer film using the etchant composition of any one of claims 1 to 9.

(1) forming a gate wiring on a substrate; (2) forming a gate insulating layer on a substrate including the gate wiring; (3) forming an oxide semiconductor layer on the gate insulating layer; (4) forming source and drain electrodes on the oxide semiconductor layer; And (5) forming a pixel electrode connected to the drain electrode, wherein the step (5) comprises forming a multi-layer film, etching the multi-layer film with the etchant composition, And forming a multi-film etching liquid composition of the present invention, which comprises the above-described multi-layered etching liquid composition of the present invention.

The present invention provides an etchant capable of batch etching with only the etchant composition of the present invention without any other process or other etchant solution in order to realize multifunctional wirings made of various kinds of metal and multi- And an object of the present invention is to provide an etchant composition for a multi-layer film.

The present invention relates to a process for the preparation of a four-layer film consisting of a titanium / indium oxide / aluminum / indium oxide film as well as a double film, triple film, consisting of titanium / copper or titanium / copper / titanium with the etchant composition of the present invention alone, Batch etching is possible.

1 is a diagram related to the results of a multi-film etching experiment.

The present invention relates to an etchant composition for a multi-layer film and an etching method using the same, wherein A) persulfate, B) fluorine compound, C) inorganic acid, D) organic acid E) organic acid salt, F) (H) glycine, it is possible to collectively etch multiple films in a wet manner, thereby shortening the time of the entire process to maximize efficiency and to reduce cost. Thin film transistors - An etching method using the same, and a method of manufacturing an array substrate for a display device using the same.

The multi-membranes of the present invention refer to multi-membranes of more than triple membranes, and may be triple membranes, quasar membranes, pseudomembranes, or mass membranes. Preferably, the multiple membrane may be a quadruple membrane, and more specifically may comprise one or more membranes comprising one or more of titanium, indium oxide, and silver. Examples of the multi-layer of the present invention include, but are not limited to, a quadruple layer composed of a titanium / indium oxide / silver / indium oxide layer.

The indium oxide film of the present invention is not limited to indium tin oxide (ITO), zinc oxide indium (IZO), zinc indium tin oxide (ITZO), gallium indium zinc oxide (IGZO)

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

A) Persulfate

The persulfate of the present invention serves as an oxidizing agent for the metal film.

The persulfate of the present invention may be present at from about 0.5% to about 20.0% by weight, preferably from 5.0% to 12.0% by weight, based on the total weight of the composition. If the amount of the persulfate is less than the above range, the etching rate may be decreased and sufficient etching may not be performed. If the amount of the persulfate is larger than the above range, it is difficult to control the etching degree because the etching rate is excessively high, so that the metal film may be overetching.

Examples of the persulfate include potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and / or ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) , And the like, but is not limited thereto.

B) Fluorine compound

The fluorine compound etches a titanium film or the like included in the multi-layer film and removes residues that may be generated by the etching.

The fluorine compound may be contained in an amount of about 0.01 wt% to about 2.0 wt%, preferably 0.1 wt% to 1.0 wt%, based on the total weight of the etchant composition. If the content of the fluorine compound is lower than the above range, etching of titanium is difficult and the frequency of occurrence of residue is increased. If it is higher than the above range, damage to the laminated glass substrate may occur.

The fluorine compound may be, for example, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and / Potassium bifluoride, and the like, but is not limited thereto.

C)

The inorganic acid is a co-oxidant. The etching rate can be controlled according to the content of the inorganic acid in the etchant composition. The inorganic acid may react with Ag ions in the etchant composition, thereby preventing the Ag ion from being increased and preventing the etching rate from decreasing.

The inorganic acid is contained in an amount of about 5.0 wt.% To about 15.0 wt.%, Preferably about 10.0 to 15.0 wt.%, Based on the total weight of the etchant composition. If the content of the inorganic acid is lower than the above range, the etching rate is decreased and a sufficient etching rate is not attained. If the content of the inorganic acid is higher than the above range, a crack may be generated in the photoresist film used for metal film etching or the photoresist film may be peeled off. When the photoresist layer is cracked or the photoresist layer is peeled off, the indium oxide layer or the Ag layer under the photoresist layer is excessively etched.

The inorganic acid may include, but is not limited to, at least one selected from the group consisting of nitric acid, sulfuric acid, and / or perchloric acid.

D) Organic acid

The organic acid increases the etching rate of all the metal films as the content in the etchant increases. The organic acid may be contained in an amount of about 10.0 to about 30.0 wt%, preferably about 15.0 wt% to about 30.0 wt%, based on the total weight of the etchant composition. When the content of the organic acid is lower than the above range, the etching rate is lowered. When the content of the organic acid is higher than the above range, the etching rate is increased and the taper angle is higher than intended.

The organic acid may be selected from the group consisting of tartaric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, malonic acid, pentanoic acid and / or oxalic acid, and the like, but the present invention is not limited thereto.

E) Organic acid salt

The organic acid salt lowers the etching rate as the content in the etchant increases. In particular, it acts as a chelate to form a complex with metal ions in the etchant composition to control the etch rate of the metal. The organic acid salt is contained in an amount of about 0.1% by weight to 10.0% by weight, preferably 0.5% by weight to 5.0% by weight, based on the total weight of the etchant composition. If the content of the organic acid salt is lower than the above range, it is difficult to control the etching rate of copper, and an over-etching angle may occur. If the content is higher than the above range, the etching rate of copper is lowered and the etching time in the process becomes longer. As a result, the number of substrates to be processed decreases.

The organic acid salt may be at least one selected from the group consisting of tartaric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, sodium salt and ammonium salt of the group consisting of malonic acid, pentanoic acid and / or oxalic acid, and it is preferably selected from the group consisting of potassium acetate, sodium acetate, And ammonium acetate, and it is not limited thereto.

F) Ring type Amine  compound

The cyclic amine compound can be used as a corrosion inhibitor. The cyclic amine compound is contained in an amount of about 0.1 wt% to about 5.0 wt%, preferably 0.3 wt% to 3.0 wt%, based on the total weight of the etchant composition. If the content of the cyclic amine compound is lower than the above range, the etching rate of the metal film becomes higher and there is a risk of overexposure. If the content is higher than the above range, the etching rate of the metal film may be lowered and the desired etching may not be achieved.

The cyclic amine compound may be, for example, an aminotetrazole, an imidazole, an indole, a purine, a pyrazole, a pyridine, a pyrimidine, And may include pyrrole, pyrrolidine and / or pyrroline. Or the cyclic amine compound may include a mixture of two or more of them.

G) Sulfamic acid ( Sulfamic  acid)

Sulfamic acid serves as an antidegradant additive and plays a role in maintaining the initially intended taper angle. The sulfamic acid is contained in an amount of about 0.1% by weight to about 6.0% by weight, preferably 1.0% by weight to 5.0% by weight, based on the total weight of the etching composition. If the content of sulfamic acid is less than about the above range, it does not play the role of maintaining the etching shape, and the replacement period of the chemical solution becomes short. If it exceeds the above range, the etching rate becomes too fast,

H) glycine ( Glycine )

Glycine maintains the corrosion inhibitor for the metal film and the amount of side etch originally intended. There is no change with time of the component itself, and it also plays a role of stabilizing the chemical solution by chelating the metal ions eluted in the chemical solution well. The glycine is contained in an amount of about 0.1% to about 5.0% by weight based on the total weight of the etchant composition. If the content of glycine is lower than about 0.1 wt%, the chelating effect against the metal ions eluted from the metal film is deteriorated, and the stability of the chemical solution is decreased. If the glycine content is higher than 5.0 wt%, the etching rate for the metal film is lowered, It grows longer. Preferably 0.1% by weight to 3.0% by weight.

The present invention relates to a method for producing a compound represented by the general formula (1) or (2), which is used in the present invention, in which A) persulfate, B) fluorine compound, C) inorganic acid, D) organic acid E) , And it is preferable that the etchant composition of the present invention has purity for semiconductor processing.

The present invention also provides a method of manufacturing a light-emitting device, comprising the steps of (1) forming a multi-layer on a substrate, (2) selectively leaving a multi- And (3) etching using the etchant composition of the present invention; To provide a multi-layer etch process.

The present invention also provides a method of manufacturing a semiconductor device, comprising: (1) forming a gate wiring on a substrate; (2) forming a gate insulating layer on the substrate including the gate wiring; (3) forming an oxide semiconductor layer on the gate insulating layer; (4) forming source and drain electrodes on the oxide semiconductor layer; And (5) forming a pixel electrode connected to the drain electrode; (5) comprises forming a multilayer film and etching the multilayer film with an etchant composition to form a pixel electrode, wherein the etchant composition is formed by a method comprising the steps of: The present invention also provides a method of manufacturing an array substrate for a display device, which is an etching liquid composition of the present invention.

The multi-layered etchant composition of the present invention can etch not only a double layer but also a multi-layered film having a triple layer or more and a sub-multi-layered film, and the quadruple in the multi-layered film is preferably a quadruple layer composed of a titanium / indium oxide / aluminum / , But is not limited thereto.

In the present invention, the indium oxide film may be at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium indium gallium indium (IGZO) But is not limited thereto.

The above-described etching solution composition of the present invention is equally applied to the above-mentioned multi-film etching method and the manufacturing method of the array substrate for a display device.

< Etchant  Composition Preparation>

10 kg of each of the etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 8 was prepared according to the composition shown in Table 1 below and the remaining amount of water was included so that the total weight of the etching solution composition was 100% by weight.

[Table 1]

Experimental Example  One: Multi-membrane Etching  evaluation

It is an experimental condition to determine whether batch etching can be performed on each of the chemical compositions after keeping each chemical solution at 30 ° C. Etcher uses equipment (Mini Etching Station, AST) that can process 0.5G glass size, chemical spray is spray type and spray pressure is 0.1MPa. The exhaust pressure in the etcher zone is maintained at 20 Pa. The etching temperature was 30 ° C. and the etching time was 60% over etching (OverEtch = 60%) based on the time when the lower film Ti was etched. The film structure of the quaternary membrane prepared for the experiment is a quaternary film deposited from the bottom in the order of titanium (Ti) / indium oxide film (IZO) / aluminum (Al) / indium oxide film (IZO).

[Table 2]

The difference (step difference) to each etching amount was measured based on aluminum. When the Ti, the lower IZO, and the upper IZO are the same with respect to the aluminum as the etching amount, all of the steps become '0', and the ideal IZO becomes the ideal batch etching. In this experiment, the lower IZO and the upper IZO, Table 2 shows the result obtained by SEM measurement after the etching of the quaternary film by composition. In the case of Examples 1 to 3, the difference in etching of the aluminum film as the main layer and the indium oxide film (IZO) deposited on the upper and lower sides with respect to the aluminum film as the center is very small and can be collectively etched. On the other hand, in Comparative Examples 1 to 5, the etching rates of aluminum and indium oxide films are different, and the remaining amount of indium oxide film located on the upper and lower sides of the aluminum film is large. Generally, when the thickness is larger than 0.1 mu m, wire breakage or short-circuiting may occur in a subsequent process, so that the composition of Comparative Examples 1 to 8 is not applicable to the process.

Claims (11)

A) from about 0.5% to about 20.0% by weight of persulfate;
B) from about 0.01% to about 2.0% by weight of a fluorine compound;
C) from about 5.0% to about 15.0% by weight of an inorganic acid;
D) from about 10.0 to about 30.0% by weight of organic acid;
E) from about 0.1% to 10.0% by weight of an organic acid salt;
F) from about 0.1% to about 5.0% by weight of a cyclic amine compound;
G) from about 0.1% to about 6.0% by weight of sulfamic acid;
H) glycine about 0.1 wt% to about 5.0 wt%; And
I) balance of water.
The method of claim 1, wherein the persulfate is selected from the group consisting of potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) And at least one selected from the group consisting of the fluorine-containing compound and the fluorine-containing compound.
The method of claim 1, wherein the fluorine compound is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride). &lt; / RTI &gt;
The etchant composition according to claim 1, wherein the inorganic acid comprises at least one selected from the group consisting of nitric acid, sulfuric acid, and perchloric acid.
The method of claim 1, wherein the organic acid is selected from the group consisting of tartaric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid ), Malonic acid, pentanoic acid, and oxalic acid. &Lt; Desc / Clms Page number 13 &gt;
The organic acid salt according to claim 1, wherein the organic acid salt is selected from the group consisting of tartaric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, a sodium salt and an ammonium salt of a group selected from the group consisting of hydrochloric acid, hydrobromic acid, malonic acid, pentanoic acid and oxalic acid, and the like. Etchant composition for a film.
The etchant composition of claim 1, wherein the multilayer is a triplet or more and a submicrometer.
The multilayer etchant composition of claim 1, wherein the multilayer film is a quadruple film composed of a titanium / indium oxide / aluminum / indium oxide film.
The method of claim 8, wherein the indium oxide film is at least one selected from the group consisting of indium tin oxide (ITO), zinc oxide indium (IZO), zinc tin indium (ITZO), and gallium gallium indium (IGZO) Etchant composition.
(1) forming a multi-layer on a substrate;
(2) selectively leaving a photoreactive material on the multiple layers; And
(3) A multi-layer etch process comprising etching the multi-layer using the etchant composition of any one of claims 1 to 9.
(1) forming a gate wiring on a substrate;
(2) forming a gate insulating layer on the substrate including the gate wiring;
(3) forming an oxide semiconductor layer on the gate insulating layer;
(4) forming source and drain electrodes on the oxide semiconductor layer; And
(5) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The step (5) includes forming a multi-layer film and etching the multi-layer film with an etchant composition to form a pixel electrode,
Wherein the etching liquid composition is the multi-film etching liquid composition according to any one of claims 1 to 9.

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