KR20110054408A - Manufacturing method of an array substrate for liquid crystal display - Google Patents

Abstract

PURPOSE: A manufacturing method of an array substrate for a liquid crystal display is provided to increase production yield by simplifying the manufacturing process. CONSTITUTION: A method for manufacturing an array substrate comprises steps of: forming a gate wiring on a substrate; forming a gate insulating layer on the substrate; forming a semiconductor layer on the gate insulating layer; forming a source and a drain electrodes on the semiconductor layer; and forming a pixel electrode which are connected to the source and the drain electrodes.

Description

Manufacturing method of array substrate for liquid crystal display device {MANUFACTURING METHOD OF AN ARRAY SUBSTRATE FOR LIQUID CRYSTAL DISPLAY}

The present invention provides a method of manufacturing an array substrate for a liquid crystal display device, an etching liquid composition of a double film consisting of a copper metal film and a titanium metal film, and an etching of a double film consisting of a copper metal film and a titanium metal film using the etching liquid composition. It is about a method.

The process of forming the metal wiring on the substrate in the semiconductor device is generally composed of a metal film forming process by sputtering or the like, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. And washing processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically, a dry etching using a plasma or the like and a wet etching using an etching liquid composition are used.

In such semiconductor devices, the resistance of metallization has recently emerged as a major concern. Since resistance is a major factor causing RC signal delay, especially for TFT LCD (thin film transistor liquid crystal display), it is a key to increasing panel size and realizing high resolution. Therefore, in order to realize the reduction of RC signal delay, which is essential for the large-sized TFT LCD, low-resistance material development is essential, and chromium (Cr, specific resistance: 12.7 × 10 ^-8 Ωm), molybdenum ( Mo, resistivity: 5 x 10 ^-8 mm, aluminum (Al, resistivity: 2.65 x 10 ^-8 mm), and alloys thereof are difficult to use for gate and data wiring used in large-sized TFT LCDs.

Under such a background, there is a high interest in a double film made of a copper-based metal film and a titanium-based metal film and an etching liquid composition thereof as the metal film under consideration.

On the other hand, the etchant compositions known to date as an etchant for a double layer consisting of such a copper-based metal film and a titanium-based metal film does not meet the performance required by the user, and research and development for improvement thereof is required.

That is, the etching liquid compositions currently used mainly use peroxides such as hydrogen peroxide or persulfate as main oxidizing agents, causing a problem of deterioration of storage stability due to self-decomposition of the peroxides. In addition, when hydrogen peroxide is used as the main oxidizing agent, a chain decomposition reaction of hydrogen peroxide occurs as the copper ion concentration in the etching solution increases during etching, thereby causing a risk of overheating.

Accordingly, the present invention provides an etching solution composition of a double layer consisting of a copper-based metal film and a titanium-based metal film, which has excellent storage stability and maintains excellent etching characteristics for a long time, and is free from danger of overheating caused by the use of hydrogen peroxide as the main oxidizing agent. It aims to provide.

In addition, the present invention provides a tapered profile having excellent linearity during etching and no residue is left, and a double film made of a copper-based metal film and a titanium-based metal film capable of collective etching of gate electrodes, gate wirings, data electrodes, and data wirings. It is an object to provide an etchant composition.

In addition, an object of the present invention is to provide an etching method of a double film consisting of a copper-based metal film and a titanium-based metal film using the etchant composition and a method of manufacturing an array substrate for a liquid crystal display device.

The present invention, based on the total weight of the composition

A) 0.5-20 wt% persulfate compound;

B) 0.01 to 2.0% by weight of a compound wherein fluorine ions dissociate in solution;

C) 0.01 to 5.0 wt% of a cyclohexylamine compound unsubstituted or substituted with one or more C1 to C4 straight or branched alkyl groups; And

D) It provides an etching solution composition of a double film comprising a residual amount of water, a copper-based metal film and a titanium-based metal film containing no hydrogen peroxide.

In addition,

I) forming a double film made of a copper-based metal film and a titanium-based metal film on the substrate;

II) selectively leaving a photoreactive material on the double layer consisting of the copper-based metal film and titanium-based metal film; And

III) an etching method of a copper-based metal film comprising etching the double layer consisting of the copper-based metal film and the titanium-based metal film using the etchant composition of the present invention.

In addition, 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 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;

In the step a), after forming a double layer consisting of a copper-based metal film and a titanium-based metal film on the substrate, the gate wiring is formed by etching with the etchant composition of the present invention, and in step d), the copper-based metal film and titanium A method of manufacturing an array substrate for a liquid crystal display device is provided by forming a double layer made of a metal layer and then etching the etching liquid composition to form a source and a drain electrode.

The present invention also provides an array substrate for a liquid crystal display device including at least one of a gate wiring and a source and a drain electrode etched using the etchant composition.

The etchant composition of the present invention is excellent storage stability is maintained excellent etching characteristics for a long time, and provides an effect without the risk of overheating caused by the use of hydrogen peroxide.

In addition, when etching the double layer consisting of a copper-based metal film and a titanium-based metal film with the etchant composition of the present invention, a taper profile having excellent linearity is formed and no residue of the copper-based metal film is left. Can be free from problems such as

In addition, since it is possible to collectively etch the gate electrode, the gate wiring, the data electrode and the data wiring using only the etchant composition according to the present invention, the process may be very simplified and the process yield may be maximized.

In addition, when using the etchant composition according to the present invention, it is possible to implement a large-screen, high-brightness circuit using a low-resistance copper or copper alloy wiring and to manufacture an environmentally friendly semiconductor device.

The present invention relates to a composition comprising: A) a persulfate compound, B) a compound in which fluorine ions dissociate in a solution, C) a cyclohexylamine compound unsubstituted or substituted with one or more C1 to C4 straight or branched alkyl groups, and D) water It includes, and relates to an etching solution composition of a double film consisting of a copper-based metal film and a titanium-based metal film does not contain hydrogen peroxide.

In the present invention, the copper-based metal film means a copper film or a copper alloy film (including an oxide film and a nitride film of copper), and the titanium-based metal film means a titanium film or a titanium alloy film. The double layer including the copper-based metal film and the titanium-based metal film may include, for example, a "titanium-based metal film / copper-based metal film" and a titanium-based metal film having a copper-based metal film as a lower film and a titanium-based metal film as an upper film. And a double film of " copper metal film / titanium metal film " having a lower film and a copper metal film as an upper film. The double layer may determine the structure of the double layer by considering the material of the film disposed on the upper portion of the membrane, the material constituting the membrane disposed below, or the adhesiveness with the films. In addition, the copper film and the titanium film are not limited in thickness to each other, and various combinations are possible. For example, the thickness of the copper film may be larger than that of the titanium film, or may be small.

Persulfate is the main component for etching the copper-based metal film. Specific examples of the persulfate include potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), and the like. One kind alone or two or more kinds may be used together.

The content of the persulfate is preferably 0.5 to 20% by weight based on the total weight of the composition. If the content of the persulfate is less than 0.5% by weight, the copper-based metal may not be etched or the etching rate is very slow. If the content of the persulfate exceeds 20% by weight, the process may be difficult to control because the etching rate may be faster.

The compound in which fluorine ions are dissociated in the solution is a main component for etching the titanium-based metal film, and serves to remove residues that may occur during etching. As the compound in which fluorine ions dissociate in the solution, a compound in which fluorine ions or polyatomic fluorine ions dissociate in the solution can be used without particular limitation. Preferably ammonium fluoride, sodium fluoride, potassium fluoride and the like and their heavy fluoride compounds, that is, ammonium bifluoride, sodium bifluoride, potassium bifluoride (potassium bifluoride) and the like, and these may be used alone or in combination of two or more.

The content of the compound in which the fluorine ions dissociate in the solution is preferably 0.01 to 2.0% by weight based on the total weight of the composition. When the content of the compound is less than 0.01% by weight, the etching rate of the titanium-based metal film may be lowered, resulting in residue. Exceeding the wt% may damage the substrate (Glass, etc.) and the insulating film (silicon film, etc.).

The cyclohexylamine compound substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups serves to slow down the decomposition rate of persulfate. Specific examples of the cyclohexylamine compound substituted or unsubstituted with at least one C1 to C4 linear or branched alkyl group include compounds represented by the following general formula (1).

[Formula 1]

In the above formula, R1 and R2 are each independently hydrogen or a C1-C4 linear or branched alkyl group.

As said C1-C4 linear or branched alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, tert- butyl group, etc. are mentioned.

The content of the cyclohexylamine compound substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups is preferably 0.01 to 5.0% by weight based on the total weight of the composition, and when less than 0.01% by weight, decomposition of hydrogen peroxide The speed inhibiting power is lowered, the etching rate is lowered when it exceeds 5.0% by weight.

Although the said water is not specifically limited, Deionized water is preferable. More preferably, deionized water having a specific resistance value of the water (that is, the degree to which ions are removed in the water) is 18 kW / cm or more is used.

The etching solution composition according to the present invention may include a glycol ether compound in addition to the aforementioned components. Glycol ether compounds serve to assist the persulfate stabilizing effect of cyclohexylamine, and at the same time serves to decrease the surface tension to increase the uniformity of etching.

Specific examples of glycol ethers include glycerol, ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), and polyethylene glycol (PEG). And polypropylene glycol (PPG) etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.

The content of the glycol ether compound is preferably 0.01 to 4% by weight based on the total weight of the composition, when less than 0.01% by weight, the etching uniformity is lowered, if more than 4% by weight has a disadvantage of generating a lot of bubbles.

In the etching liquid composition according to the present invention, a conventional additive may be further added in addition to the above components, and as the additive, a metal ion blocking agent, a corrosion inhibitor, and the like may be used.

Persulfates used in the present invention, compounds in which fluorine ions dissociate in solution, cyclohexylamine compounds substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups may be prepared by a conventionally known method. And it is preferable to have the purity for a semiconductor process.

The etching liquid composition of the double layer consisting of the copper-based metal film and the titanium-based metal film according to the present invention is a gate electrode, gate wiring, data electrode and data wiring of the liquid crystal display device consisting of a double-layer made of a copper-based metal film and a titanium-based metal film. Batch etching can be performed.

In addition, the present invention,

I) forming a double film made of a copper-based metal film and a titanium-based metal film on the substrate;

II) selectively leaving a photoreactive material on the double layer consisting of the copper-based metal film and titanium-based metal film; And

III) Etching method of the copper-based metal film comprising etching the double layer consisting of the copper-based metal film and titanium-based metal film using the etching liquid composition of the present invention.

In the etching method of the present invention, the photoreactive material is preferably a conventional photoresist material, and may be selectively left by conventional exposure and development processes.

In addition, 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 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;

In the step a), after forming a double layer consisting of a copper-based metal film and a titanium-based metal film on the substrate, the gate wiring is formed by etching with the etchant composition of the present invention, and in step d), the copper-based metal film and titanium The present invention relates to a method of manufacturing an array substrate for a liquid crystal display device, after forming a double layer made of a metal layer, and then etching the etching solution composition to form source and drain electrodes.

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

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.

Example 1 and Comparative Example 1: Preparation of etching liquid composition and evaluation of etching characteristics

To the etchant composition of Example 1 and Comparative Example 1 according to the composition shown in Table 1. Then, the etching process of the Cu / Ti double layer using the etching solution composition.

<Etch Characteristic Evaluation>

The etching liquid composition of Example 1 to Comparative Example 1 was placed in an experimental equipment of a spray etching method (manufacturer: SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C. and heated. Then, after the temperature reached 30 ± 0.1 ℃, the etching process was performed. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper. After washing and drying, using an electron scanning microscope (SEM; manufacturer: HITACHI, model name: S-4700) to evaluate the residue and etching characteristics, the results are shown in Table 1 below.

<Stability Evaluation>

After storing the etching solution of Examples 1 to Comparative Example 1, which performed the etching characteristic evaluation, the substrates were etched one by one after 3, 7, and 15 days from the first etching, respectively, to evaluate storage stability. . Long-term storage of the prepared etchant composition was repeated to evaluate the etching characteristics, the change in the etching performance of the long-term storage was evaluated.

As shown in the evaluation results of Table 1, the etching solution (Example 1) of the present invention containing a cyclohexylamine compound compared to the etching solution (Comparative Example 1) does not contain a cyclohexylamine compound has excellent storage stability It could be confirmed.

Claims (12)

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 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; In step a), a double layer including a copper-based metal film and a titanium-based metal film is formed on the substrate, followed by etching with an etchant composition to form a gate wiring, and in step d), the copper-based metal film and the titanium-based metal film. After forming a double layer consisting of, by etching with an etchant composition to form a source and drain electrode, The etchant composition, A) 0.5 to 20% by weight based on the total weight of the composition; B) 0.01 to 2.0% by weight of a compound wherein fluorine ions dissociate in solution; C) 0.01 to 5.0 wt% of a cyclohexylamine compound unsubstituted or substituted with one or more C1 to C4 straight or branched alkyl groups; And D) a residual amount of water, and does not include hydrogen peroxide. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the array substrate for liquid crystal display device is a thin film transistor (TFT) array substrate. A) from 0.5 to 20% by weight, based on the total weight of the composition; B) 0.01 to 2.0% by weight of a compound wherein fluorine ions dissociate in solution; C) 0.01 to 5.0 wt% of a cyclohexylamine compound unsubstituted or substituted with one or more C1 to C4 straight or branched alkyl groups; And D) a copper-based metal film and a titanium-based metal film containing a residual amount of water and comprising no hydrogen peroxide. The method according to claim 3, wherein the persulfate is 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 ) An etching solution composition of a double film consisting of a copper-based metal film and a titanium-based metal film, characterized in that one or two or more selected. The method of claim 3, wherein the fluorine ions dissociate in the solution is ammonium fluoride (sodium fluoride), sodium fluoride (sodium fluoride), potassium fluoride (potassium fluoride), ammonium bifluoride, sodium bifluoride (sodium Bifluoride), and potassium bifluoride (potassium bifluoride) is one or more selected from the group consisting of a copper-based metal film and an etching liquid composition of a double film consisting of a titanium-based metal film. The etchant composition according to claim 3, wherein the etchant composition further comprises 0.01 to 4% by weight of a glycol ether compound based on the total weight of the composition. The method according to claim 6, wherein the glycol ether compound is glycerol (glycerol), ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), dipropylene glycol (DPG), polyethylene An etching solution composition of a double layer consisting of a copper-based metal film and a titanium-based metal film, characterized in that one or two or more selected from the group consisting of glycol (PEG) and polypropylene glycol (PPG). The double film according to any one of claims 3 to 7, wherein the double film made of a copper metal film and a titanium metal film is a double film made of a copper film or a copper alloy film (including an oxide film of copper and a nitride film) and a titanium film or a titanium alloy film. An etching liquid composition of a double layer consisting of a copper-based metal film and a titanium-based metal film, characterized in that the. I) forming a double film made of a copper-based metal film and a titanium-based metal film on the substrate; II) selectively leaving a photoreactive material on the double layer consisting of the copper-based metal film and titanium-based metal film; And III) Etching the double layer consisting of the copper-based metal film and titanium-based metal film comprising the step of etching the double layer consisting of the copper-based metal film and titanium-based metal film using the etching liquid composition of any one of claims 3 to 7. Way. 10. The method of claim 9, wherein the photoreactive material is a photoresist material, and is selectively left by an exposure and development process. The double film made of a copper metal film and a titanium metal film is a double film made of a copper film or a copper alloy film (including an oxide film of copper and a nitride film) and a titanium film or a titanium alloy film. An etching method of a double layer consisting of a copper-based metal film and a titanium-based metal film. An array substrate for a liquid crystal display device comprising at least one of a gate wiring and a source and drain electrode etched using the etchant composition according to claim 3.