TW201627473A - Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same - Google Patents

Abstract

The present invention relates to an etching solution composition for an indium oxide layer and a method for manufacturing an array substrate for a liquid crystal display device using the same, and more particularly, to an etching solution composition for an indium oxide layer not including a sulfate or acetate, but including nitric acid, an azole compound, a fluorine-containing compound and water, a method for manufacturing an array substrate for a liquid crystal display device using the same.

Description

Indium oxide layer etching liquid composition and method for manufacturing array substrate of liquid crystal display device therewith Technical field

The present invention relates to an indium oxide layer etchant composition and a method of manufacturing the same using the array substrate of the liquid crystal display device, and more particularly, it does not include sulfate or acetate, but includes nitric acid, an azole compound, a fluorine-containing compound, and An indium oxide layer etching solution composition of water, and a method of manufacturing an array substrate of a liquid crystal display device using the same.

Background technique

Liquid crystal display devices (LCDs) are the most popular among flat panel display devices because they provide sharp images with excellent resolution, consume less energy, and can thin the display screen. A typical electronic circuit that drives such liquid crystal display devices today is a thin film transistor (TFT) circuit, and a typical thin film transistor liquid crystal display device (TFT-LCD) forms pixels of a display screen. A TFT functioning as a switching device in a TFT-LCD fills a substrate of a TFT arranged in a matrix form with a liquid crystal material and a color facing the TFT substrate Manufactured by the space between the filter substrates. The complete TFT-LCD manufacturing process is generally divided into a TFT substrate manufacturing process, a color filter process, a unit process, and a component process, and the TFT substrate manufacturing process and the color filter manufacturing process present an accurate and clear picture. The aspect is very important.

When manufacturing a pixel display electrode of a TFT-LCD, a film made of a material having high electrical conductivity while having transparent optical properties is required, and indium oxide-based indium tin oxide (ITO) and indium zinc oxide (IZO) are currently used as The material of the transparent conductive film.

In addition, in order to obtain a target circuit line in the pixel display electrode, it is necessary to trim the etching process of the thin film layer in accordance with the circuit pattern.

However, with the conventional etching liquid which is usually used for etching a metal double layer, it is difficult to etch a transparent conductive film made of an ITO or IZO material due to strong chemical resistance of the ITO oxide. Specifically, aqua regia (HCl + CH ₃ COOH + HNO ₃ ), a solution of ferric chloride (III) in hydrochloric acid (FeCl ₃ /HCl), or an aqueous solution of oxalic acid has been used as a wet etching solution for a transparent conductive film, however, when When the ITO layer is etched using a solution of aqua regia-based etching solution or ferric chloride in hydrochloric acid, the cost is low but the etching is faster on the side surface of the pattern, the profile is inferior, and since hydrochloric acid or nitric acid volatilizes after the formation of the etching liquid, the etching The fluctuations in the liquid composition are severe and chemical attack can occur on the lower metal. Korean Patent Application Publication No. 10-2000-0017470 etches amorphous indium tin oxide (ITO) with oxalic acid, however, in this case, residue tends to occur around the ITO pattern, and because oxalic acid has low solubility at low temperatures, The precipitate is generated, so there is a problem that the etching equipment is broken.

In addition, the etchant made of HI has a high etching rate and side surface etching It is low, but expensive, highly toxic and corrosive, and causes erosion of the data lines located at the bottom of the transparent pixel electrode, and therefore has limitations in practical use.

In addition, Korean Patent Application Publication No. 10-2010-0053175 discloses an etching composition of a transparent conductive film including a halogen-containing compound, an auxiliary oxidizing agent, an etching control agent, a residue inhibitor, a corrosion inhibitor, and water, and a sulfate and Acetate is used as an etch control agent and a residue inhibitor, respectively. However, when sulfate and acetate are included in the etching composition, the lateral etching rate is low, resulting in a small amount of side etching and a problem of underlying damage.

[Prior Art Literature]

[Patent Literature]

(Patent Document 1) Korean Patent Application Publication No. 10-2000-0017470

(Patent Document 2) Korean Patent Application Publication No. 10-2010-0053175

Summary of invention

It is an object of the present invention to maximize the efficiency of an etching process by efficiently etching an indium oxide layer at a high speed at an etchant composition that does not include one or more selected from the group consisting of sulfates and acetates.

Further, it is an object of the present invention to improve the driving performance of a thin film transistor-liquid crystal display device (TFT-LCD) by minimizing the erosion of the underlying layer of the indium oxide layer.

Accordingly, it is an object of the present invention to provide an indium oxide layer etching solution composition capable of improving the efficiency of an etching process and driving performance of a thin film transistor-liquid crystal display device (TFT-LCD), an etching method using the same, and a liquid crystal display A method of array substrate of a device.

In view of the above, an aspect of the present invention provides an indium oxide layer etchant composition which does not include one or more selected from the group consisting of sulfates and acetates, but is etched with respect to the indium oxide layer etchant composition The total weight includes 3 to 30% by weight of nitric acid, 0.1 to 10% by weight of the azole compound, and 0.01 to 5% by weight of the fluorine-containing compound, and the balance of water such that the total weight of the indium oxide layer etching solution composition It becomes 100% by weight.

Another aspect of the present invention provides a method of etching an indium oxide layer, the method comprising (1) forming an indium oxide layer on a substrate; (2) selectively leaving a photoreactive material on the indium oxide layer; (3) The indium oxide layer is etched using the indium oxide layer etching solution composition of the present invention.

Still another aspect of the present invention provides a method of manufacturing an array substrate of a liquid crystal display device, the method comprising: (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 a source and a drain on the oxide semiconductor layer; and (5) forming a pixel electrode connected to the drain, Wherein step (1) comprises forming a copper/indium oxide layer or a copper alloy/indium oxide layer on the substrate, and forming a gate wire by etching the copper/indium oxide layer or the copper alloy/indium oxide layer by using an etchant composition, The step (5) includes forming an indium oxide layer, and etching the indium oxide layer with an etching liquid composition to form a pixel electrode, and the etching liquid composition is the indium oxide layer etching liquid composition of the present invention.

Still another aspect of the present invention provides an array substrate of a liquid crystal display device comprising: an etchant selected from the group consisting of an indium oxide layer etchant using the present invention One or more of the group consisting of a gate wire and a pixel electrode.

detailed description

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

The present invention relates to an indium oxide layer etchant composition which does not include one or more selected from the group consisting of sulfates and acetates, but includes from 3 to 30 with respect to the total weight of the indium oxide layer etchant composition. The weight% of nitric acid, 0.1 to 10% by weight of the azole compound, and 0.01 to 5% by weight of the fluorine-containing compound, and the balance of water, make the total weight of the indium oxide layer etching solution composition 100% by weight.

The indium oxide layer etching solution composition of the present invention can etch the indium oxide layer at a higher rate because it does not include one or more selected from the group consisting of sulfates and acetates, and therefore, the etching process efficiency can be improved.

The indium oxide layer in the present invention includes one or more selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, and an indium gallium zinc oxide (IGZO) layer.

In addition, the indium oxide layer etched with the indium oxide layer etchant composition of the present invention may be a single layer formed of an indium oxide layer; or a plurality of layers formed of the single layer and a copper-based metal layer, and the copper-based metal layer It may be a copper layer or a copper alloy layer. The concept of the alloy layer also includes a nitride layer or an oxide layer.

The nitric acid (HNO ₃ ) included in the indium oxide layer etching liquid composition of the present invention is a main oxidizing agent of the indium oxide layer, and performs the action of etching the indium oxide layer. In addition, nitric acid has a high etch rate for the indium oxide layer and is capable of ensuring that the desired side etch is large during the etching process.

The nitric acid accounts for 3 to 30% by weight, and preferably 5 to 25% by weight, based on the total weight of the indium oxide layer etching solution composition. When the nitric acid accounts for less than 3% by weight, the etching rate of the indium oxide layer can be lowered, and when it is more than 30% by weight, the problem of chemical attack on the bottom of the indium oxide layer and the adjacent metal may occur, and The rate is too high for program control.

The azole compound included in the indium oxide layer etching liquid composition of the present invention performs the effect of minimizing the erosion of the copper wire contacting the indium oxide layer, which is used as the pixel electrode of the array substrate of the liquid crystal display device. In other words, the azole compound performs the effect of minimizing erosion of the copper-based metal layer, which is the lower layer of the indium oxide layer.

The azole compound preferably includes a compound selected from the group consisting of a triazole compound, a tetrazole compound, an imidazole compound, an anthraquinone compound, an anthraquinone compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, and a pyrrole compound. One or more of the group consisting of an alkane compound and a pyrroline compound.

Further, more specifically, the azole compound preferably comprises a group selected from the group consisting of aminotetrazole, benzotriazole, tolyltriazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2- One or more of the group consisting of aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole.

The azole compound accounts for 0.1 to 10% by weight, and preferably 0.5 to 5% by weight, based on the total weight of the indium oxide layer etchant composition. When the azole compound accounts for less than 0.1% by weight, it may be used as an indium oxide layer. The copper layer of the layer is eroded, and when it is more than 10% by weight, the erosion of the copper layer can be prevented, however, the etching rate of the indium oxide layer may be lowered.

The fluorine-containing compound included in the indium oxide layer etching liquid composition of the present invention performs the effect of removing the residue when etching the indium oxide layer.

The fluorine-containing compound is not particularly limited as long as it can be dissociated into a fluoride ion or a polyatomic fluoride ion in a solution, but preferably includes a salt selected from ammonium fluoride (NH ₄ F), sodium fluoride (NaF), and fluorine. One or more of the group consisting of potassium (KF), ammonium hydrogen fluoride (NH ₄ F.HF), sodium hydrogen fluoride (NaF.HF), and potassium hydrogen fluoride (KF.HF).

Further, the fluorine-containing compound accounts for 0.01 to 5% by weight, and preferably 0.01 to 3% by weight, based on the total weight of the indium oxide layer etching solution composition. When the fluorine-containing compound accounts for less than 0.01% by weight, a residue may occur when the indium oxide layer is etched, and when it is more than 5% by weight, there is a problem that the etching rate of the glass substrate or the tantalum layer increases.

The water included in the indium oxide layer etching solution composition of the present invention accounts for the balance such that the total weight of the composition becomes 100% by weight. The water is not particularly limited, however, it is preferred to use deionized water. In addition, it is preferred to use a specific resistance value of 18 MΩ. For deionized water of cm or higher, the specific resistance value is a value indicating the degree of ion removal in the water.

Further, the indium oxide layer etching liquid composition of the present invention may further comprise one or more selected from the group consisting of metal ion chelating agents and corrosion inhibitors. Further, the additive is not limited thereto, and in order to promote the effects of the present invention, various other additives known in the art may be selected and added.

The composition of the indium oxide layer etching solution composition of the present invention can utilize the ability The methods generally known in the art are prepared and preferably used for purity in semiconductor processes.

Further, the present invention relates to a method of etching an indium oxide layer, the method comprising (1) forming an indium oxide layer on a substrate; (2) selectively leaving a photoreactive material on the indium oxide layer; and (3) The indium oxide layer is etched using the indium oxide layer etchant composition of the present invention.

In the etching method of the present invention, the photoreactive material is preferably a commonly used photoresist material, and can be selectively left by a usual exposure and development process.

Further, the present invention relates to a method of manufacturing an array substrate of a liquid crystal display device, comprising (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 a source and a drain on the oxide semiconductor layer; and (5) forming a pixel electrode connected to the drain, wherein step (1) Forming a copper/indium oxide layer or a copper alloy/indium oxide layer on the substrate, and forming the gate wiring by etching the copper/indium oxide layer or the copper alloy/indium oxide layer by using the etching liquid composition, and the step (5) includes An indium oxide layer is formed, and the indium oxide layer is etched using an etchant composition to form a picture element electrode, and the etchant composition is an indium oxide layer etchant composition of the present invention.

The existing indium oxide layer etching solution composition including sulfate or acetate has a slow lateral etching rate, so that when the pixel electrode of the step (5) is etched, the amount of side etching is small. However, the indium oxide layer etching solution composition of the present invention does not include sulfates and acetates, whereby the problem can be solved, and To prevent erosion of the copper-based metal layer under the indium oxide layer.

The indium oxide layer formed on the substrate of the step (1) is a plurality of layers of a copper/indium oxide layer or a copper alloy/indium oxide layer, and the indium oxide layer formed in the step (5) is a single layer of an indium oxide layer.

The indium oxide layer includes one or more selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, and an indium gallium zinc oxide (IGZO) layer.

The gate wiring can be formed in the step (1) by etching with the indium oxide layer etching solution composition of the present invention, and the pixel electrode can be formed in the step (5).

The array substrate of the liquid crystal display device may be a thin film transistor (TFT) array substrate.

Further, the present invention relates to an array substrate of a liquid crystal display device comprising one or more selected from the group consisting of a gate wire and a pixel electrode etched using the indium oxide layer etchant composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the embodiments. However, the following examples are for illustrative purposes only, and the scope of the invention is not limited to the following examples. The following embodiments may be appropriately modified or changed by those skilled in the art within the scope of the invention.

<Preparation of Indium Oxide Layer Etching Solution Composition>

Examples 1 to 3 and Comparative Examples 1 to 10

The indium oxide layer etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 10 were prepared using the compositions shown in Table 1 below, and the balance of water was included so that the total weight became 100% by weight.

BTA: benzotriazole

ABF: Ammonium fluorohydride

Test Example 1. Evaluation of the properties of the indium oxide layer etching solution composition

After the source/drain is formed by depositing a copper layer on a glass substrate (100 mm x 100 mm), a hole is formed by laminating a germanium layer on the copper layer to expose the source/drain metal layer-copper. Thereafter, an indium oxide layer is deposited thereon, and a light having a prescribed pattern is formed on the substrate by a photolithography process The resist was then subjected to the etching process of the indium oxide layer using the various indium oxide layer etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 10.

A spray etching type test apparatus (model name: ETCHER (TFT), SEMES Co. Ltd.) was used, and a temperature of about 35 ° C was used for the etching liquid composition during the etching, however, the appropriate temperature may be determined if necessary. Changed by other process conditions and other factors. The etching time varies depending on the etching temperature, however, etching is usually performed for about 50 to 100 seconds during the LCD etching process. The indium oxide layer profile etched during the etching was examined by a cross-sectional SEM (product of Hitachi, Ltd., model name S-4700), and side etching, residue occurrence, glass etching rate, and lower metal (Cu) etching were observed. The results are shown in Table 2 below.

From the results of Table 2, it was confirmed that the indium oxide layer etching liquid compositions of the present invention in Examples 1 to 3 exhibited excellent side etching, no residue appeared, and excellent glass etching rate, and did not erode the underlying copper layer.

Meanwhile, the indium oxide layer etching liquid compositions of Comparative Examples 1 and 2 have a peroxide content outside the range of the present invention, which has less side etching, pattern loss, and a peroxide content smaller than that of Comparative Example 1 of the present invention. In the indium oxide layer etching liquid composition, a residue appears.

In the indium oxide layer etching liquid composition of Comparative Example 3 having a small content of the azole compound, the underlying copper layer was eroded, and in the indium oxide layer etching liquid composition of Comparative Example 4 having an excessive azole compound content, Side etching is not excellent and residue occurs.

The indium oxide layer etching liquid composition of Comparative Example 5 having an excessive content of the fluorine-containing compound had no favorable result on the glass etching rate.

Further, in the indium oxide layer etching liquid composition of Comparative Example 6 including sulfate and the indium oxide layer etching liquid composition of Comparative Example 7 including acetate, the side etching result and the glass etching result were not excellent, and the occurrence of residue was identified. .

The indium oxide layer etching liquid composition of Comparative Example 8 excluding the fluorine-containing compound, and the indium oxide layer etching liquid compositions of Comparative Examples 9 and 10 excluding the peroxide did not have excellent side etching, and all of them appeared Residue.

Therefore, the indium oxide layer etching solution composition of the present invention does not include selection One or more of the group consisting of free sulfate and acetate can increase the effect of side etching and glass etch rate.

In addition, the indium oxide layer etchant composition of the present invention does not cause residue during etching, and does not erode the copper layer under the indium oxide layer when manufacturing the array substrate of the liquid crystal display device, thereby preventing the source of the copper layer / drain breaks the defect and can effectively etch the indium oxide layer.

The indium oxide layer etching liquid composition of the present invention can effectively etch the indium oxide layer by improving the etching rate without including one or more selected from the group consisting of sulfates and acetates, and thus can improve the etching process efficiency.

In addition, the indium oxide layer etching solution composition of the present invention can minimize the erosion of the copper-based metal layer of the underlying layer of the indium oxide layer, and therefore, can enhance the driving performance of the thin film transistor-liquid crystal display device (TFT-LCD). And there is an advantage of maintaining etch uniformity even when the substrate size is large.

Claims (13)

An indium oxide layer etching solution composition which does not include one or more selected from the group consisting of sulfates and acetates, and comprises: 3 to 30 weights relative to the total weight of the indium oxide layer etching solution composition % nitric acid; 0.1 to 10% by weight of the azole compound; 0.01 to 5% by weight of the fluorine-containing compound; and the balance of water such that the total weight of the indium oxide layer etching solution composition is 100% by weight. The indium oxide layer etching solution composition according to claim 1, wherein the azole compound comprises a compound selected from the group consisting of a triazole compound, a tetrazole compound, an imidazole compound, an anthraquinone compound, an anthraquinone compound, and a pyrazole. One or more of the group consisting of a compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, and a pyrroline compound. The indium oxide layer etching solution composition according to claim 1, wherein the fluorine-containing compound comprises a group selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, sodium hydrogen fluoride, and potassium hydrogen fluoride. One or more of the groups. The indium oxide layer etching solution composition according to claim 1, wherein the indium oxide layer is a single layer formed of an indium oxide layer; or a plurality of layers formed of the single layer and a copper-based metal layer. The indium oxide layer etching solution composition according to claim 1, wherein the indium oxide layer comprises a layer selected from the group consisting of an indium tin oxide layer, an indium zinc oxide layer, and indium gallium oxide. One or more of the group consisting of zinc layers. The indium oxide layer etching solution composition according to claim 4, wherein the copper-based metal layer is a copper layer or a copper alloy layer. The indium oxide layer etching solution composition according to claim 1, which further comprises one or more selected from the group consisting of a metal ion chelating agent and a corrosion inhibitor. A method of etching an indium oxide layer, comprising: (1) forming an indium oxide layer on a substrate; (2) selectively leaving a photoreactive material on the indium oxide layer; and (3) utilizing as in claim 1 The indium oxide layer etching solution composition according to any one of the seventh aspects etches the indium oxide layer. The method of etching an indium oxide layer according to claim 8, wherein the photoreactive material is a photoresist material and is selectively left by an exposure and development process. A method of manufacturing an array substrate of a liquid crystal display device, the method comprising: (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 a source and a drain on the oxide semiconductor layer; and (5) forming a pixel electrode connected to the drain, wherein step (1) Including forming a copper/indium oxide layer or copper on the substrate An alloy/indium oxide layer, and forming a gate wire by etching the copper/indium oxide layer or a copper alloy/indium oxide layer with an etchant composition; the step (5) includes forming an indium oxide layer, and etching with an etchant composition The indium oxide layer forms a pixel electrode; and the etching liquid composition is the indium oxide layer etching liquid composition according to any one of claims 1 to 7. The method of manufacturing an array substrate of a liquid crystal display device according to claim 10, wherein the indium oxide layer comprises one or more selected from the group consisting of an indium tin oxide layer, an indium zinc oxide layer, and an indium gallium zinc oxide layer. . The method of manufacturing an array substrate of a liquid crystal display device according to claim 10, wherein the array substrate of the liquid crystal display device is a thin film transistor (TFT) array substrate. An array substrate of a liquid crystal display device comprising one or more selected from the group consisting of a gate wire and a pixel electrode etched using the indium oxide layer etchant composition according to any one of claims 1 to 7.