KR102209680B1 - Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same - Google Patents

Abstract

The present invention is a metal film oxidizing agent; Fluorine-containing compounds; Phosphoric acid; Glycols; And an etchant composition comprising the remaining amount of water, wherein the etch rate at the time of 5000 treatment sheets compared to the etch rate at the time of 100 treatment sheets is 0.9 to 1, and a liquid crystal comprising the composition A method of manufacturing an array substrate for a display device is provided.

Description

Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same

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

In the case of flat panel displays such as LCD, PDP and OLED, especially TFT-LCD, a single film made of copper or copper alloy, furthermore, copper or copper alloy, to reduce wiring resistance and increase adhesion to silicon insulating film as the screen becomes larger. The adoption of a multilayer of two or more layers of alloys/other metals, alloys of other metals, or metal oxides has been widely studied. For example, a copper/molybdenum film, a copper/titanium film, or a copper/molybdenum-titanium film can form a source/drain wire constituting a gate wire and a data line of a TFT-LCD. It can contribute to a large screen. Accordingly, there is a need to develop a composition having excellent etching properties capable of etching a metal film including the copper-based film as described above.

As for the etching composition as described above, an etching solution based on hydrogen peroxide and an amino acid, an etching solution based on hydrogen peroxide and phosphoric acid, and an etching solution based on hydrogen peroxide and polyethylene glycol are known.

For example, Korean Patent Laid-Open Publication No. 10-2011-0031796 discloses an etchant comprising A) hydrogen peroxide (H ₂ O ₂ ) B) persulfate, C) a water-soluble compound having an amine group and a carboxyl group, and water.

Republic of Korea Patent Publication No. 10-2012-0044630 discloses a copper-containing metal film etching solution containing hydrogen peroxide, phosphoric acid, a cyclic amine compound, sulfate, boronic acid and water.

Republic of Korea Patent Publication No. 10-2012-0081764 discloses an etching solution containing A) ammonium hydroxide, B) hydrogen peroxide, C) a fluorine-containing compound, D) a polyhydric alcohol and E) water.

However, the above etchants do not sufficiently satisfy the conditions required in this field in terms of CD loss, taper, pattern straightness, metal residue, storage stability, and number of processed sheets for a metal film including a copper-based film. have.

Republic of Korea Patent Publication No. 10-2011-0031796 Republic of Korea Patent Publication No. 10-2012-0044630 Republic of Korea Patent Publication No. 10-2012-0081764

The present invention is to solve the problems of the prior art as described above, and has excellent work safety, excellent etching speed, and processing capacity of a large amount of substrates, and among them, there is no decrease in the etching speed due to an increase in the number of processed sheets, so that optimal etching characteristics An object of the present invention is to provide an etchant composition for a metal film and a method of manufacturing an array substrate for a liquid crystal display using the same.

To achieve the above object,

The present invention is a metal film oxidizing agent; Fluorine-containing compounds; Phosphoric acid; Glycols; And an etchant composition containing the remaining amount of water,

It provides an etchant composition, characterized in that the etch rate at the time of 5000 sheets of treatment compared to the etch rate at the time of 100 treatment sheets is 0.9 to 1.

In addition, the present invention a) forming a gate electrode on the substrate;

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

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

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

e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,

Step a), d), or e) comprises forming a metal film, and etching the metal film with the etchant composition of the present invention to form an electrode. to provide.

The metal film etchant composition of the present invention hardly exhibits a decrease in etch rate due to an increase in the number of processed sheets, and thus, can provide an excellent number of processed sheets.

In addition, the etchant composition for a metal film comprising a copper-based film according to an embodiment of the present invention contains a low content of hydrogen peroxide as a metal oxidizing agent, thereby providing excellent work safety, cost competitiveness, and an effect of economically disposing of the etchant. Has features.

In addition, the method of manufacturing an array substrate for a liquid crystal display device using the etchant composition of the present invention is to prepare an array substrate for a liquid crystal display device having excellent driving characteristics by forming an electrode having an excellent etching profile on an array substrate for a liquid crystal display device. Makes it possible.

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

The present invention is a metal film oxidizing agent; Fluorine-containing compounds; Phosphoric acid; Glycols; And an etchant composition containing the remaining amount of water,

It relates to an etchant composition, characterized in that the etch rate at the time of 5000 treatment sheets is 0.9 to 1 compared to the etch rate at the time of 100 treatment sheets.

In the present invention, the etch rate at the time of 5,000 treatment sheets compared to the etch rate at the time of 100 treatment sheets is defined as etching endurance. In general, when etching a metal film with a metal film etchant composition, as the number of processed metal films increases, the etch rate decreases, so that a large amount of the metal film cannot be etched. However, since the etchant composition of the present invention is excellent in etching endurance, it has the advantage of being able to etch more metal films since a decrease in etch rate due to an increase in the number of processed sheets hardly occurs. In the above, the etch rate refers to a value obtained by measuring the time until all metal films of a certain thickness are etched, and dividing the thickness of the metal by the time (metal thickness/time, μm/sec).

The etching endurance of the etchant composition of the present invention cannot exceed 1, and if it is less than 0.9, problems such as an etching residue and a change in taper angle due to a difference in etching rate under the same process conditions occur.

The metal film oxidizing agent is not particularly limited as a main component that oxidizes the metal of the metal film, and representatively may be at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid and halide. have.

The metal oxide refers to an oxidized metal, for example, Fe ^{3 +} , Cu ^{2 +,} etc., and the metal oxide also includes a compound that dissociates into the Fe ^{3 +} , Cu ^{2 +} etc. in a solution state, and Sulfate includes ammonium persulfate, persulfate alkali metal salt, oxone, and the like, and halide includes chlorate, perchlorate, bromate, perbromate, and the like.

The etchant composition comprises 1 to 40% by weight of a metal layer oxidizing agent based on the total weight of the composition; 0.1 to 5% by weight of a fluorinated compound; 0.01 to 10% by weight of phosphoric acid; 0.1 to 10% by weight of glycols; And the remaining amount of water.

The content of the metal layer oxidizing agent may be appropriately adjusted according to the type and characteristics of the oxidizing agent, and if it is included in the above range, the etch rate of the metal layer may be appropriately adjusted.

The fluorinated compound is preferably contained in an amount of 0.1 to 5% by weight, more preferably 0.1 to 2% by weight, based on the total weight of the composition. If the above-described range is satisfied, it is preferable because the etching residue is prevented and the etching of the glass substrate or the lower silicon film is not caused. However, outside the above-described range, stains may occur in the substrate due to non-uniform etching characteristics, the lower layer may be damaged due to an excessive etching rate, and it may be difficult to control the etching rate during processing.

The fluorine-containing compound is preferably a compound capable of dissociating into fluorine ions or polyatomic fluorine ions. The compound capable of dissociating into the fluorine ion or the polyatomic fluoride ion may be one or two or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, sodium bifluoride, and potassium bifluoride.

The phosphoric acid may be included in an amount of 0.01 to 10% by weight, more preferably 0.01 to 1% by weight, based on the total weight of the composition. When the phosphoric acid satisfies the above-described range, it is possible to avoid the risk of excessive etching of the metal layer due to the phosphoric acid and corrosion of the lower layer, and there is no problem that the etching rate of the copper metal layer is lowered because the content of phosphoric acid is too low. It can perform its original function.

As the glycols, components known in the art may be used without limitation, and in particular, polyethylene glycol may be preferably used.

Polyethylene glycol is an addition polymer of ethylene oxide, and it is possible to have either a hydroxy group or an ether group, but at least one is preferably a hydroxy group.In order to suppress an excessive increase in the viscosity of the solution, the molecular weight is more than 1000. desirable.

The content of the glycols is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the composition. When the content of glycols is less than 0.1% by weight, it is difficult to expect an effect of improving the number of processed substrates, and a problem of lowering the etching uniformity may occur. If it exceeds 10% by weight, a lot of bubbles are generated. Disadvantages can occur.

The etchant composition of the present invention may be preferably used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of them.

The copper-based metal film refers to a copper film or a copper alloy film, the molybdenum-based metal film refers to a molybdenum film or a molybdenum alloy film, and the titanium-based metal film refers to a titanium film or a titanium alloy film.

The multilayer film may include, for example, a double layer of a molybdenum-based metal film/copper-based metal film having a copper-based metal film as a lower film and a molybdenum-based metal film as an upper film; A copper-based metal film with a molybdenum-based metal film as a lower film and a copper-based metal film as an upper film/double film of a molybdenum-based metal film, a copper-based metal film/double film of a molybdenum-based and titanium-based alloy film, and molybdenum A triple layer in which a copper-based metal film and a molybdenum-based metal film are alternately stacked, such as a nium-based metal film/copper-based metal film/molybdenum-based metal film, or a copper-based metal film/molybdenum-based metal film/copper-based metal film It includes more than one membrane.

In addition, the multilayer film is, for example, a copper-based metal film as a lower film, a titanium-based metal film as an upper film, a titanium-based metal film/copper-based metal film as a double film, a titanium-based metal film as a lower film, and a copper-based metal film as an upper film. A copper-based metal film/titanium-based metal film, a copper-based metal film/titanium-based metal film, and a molybdenum-based alloy film and a titanium-based metal film/copper-based metal film/titanium-based metal film or a copper-based metal Like a film/titanium-based metal film/copper-based metal film, it includes a triple or more multilayer in which a copper-based metal film and a titanium-based metal film are alternately stacked.

In the multilayer film, the interlayer bonding structure may be determined in consideration of a material constituting a film disposed above or below the multilayer film, or adhesion with the films.

In the above, the copper, molybdenum, or titanium alloy film refers to a metal film made of an alloy using copper, molybdenum, or titanium as a main component according to the characteristics of the film. For example, the molybdenum alloy film contains molybdenum as a main component, and at least one selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In) It means a film made of an alloy formed including.

The etchant composition of the present invention may further include a nitrogen atom-containing compound.

The nitrogen atom-containing compound contained in the etchant composition of the present invention serves to improve the etch rate and the number of processed sheets of the etchant. As the nitrogen atom-containing compound, those known in the art may be used without limitation, and representatively, a compound containing an amino group and a carboxylic acid group in a molecule may be used,

Compounds containing an amino group and a carboxylic acid group in the molecule include an alpha amino acid containing one carbon atom between the carboxylic acid and the amino group, and representatively monovalent amino acids such as glycine, glutamic acid, glutamine, isoleucine proline, tyrosine, arginine, etc. And polyhydric amino acids such as iminodiacetic acid, nitrilodriacetic acid, and ethylene glycol tetraacetic acid. The nitrogen atom-containing compounds may be used alone or in combination of two or more.

The nitrogen atom-containing compound may be included in an amount of 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. When the nitrogen atom-containing compound is included in the above-described range, the etching rate of the etching solution and the number of processed sheets can be improved.

The water used in the present invention means deionized water and is used for semiconductor processing, and preferably, water of 18㏁/cm or more is used.

The etchant composition of the present invention may further include at least one of an etch control agent, a surfactant, a metal ion sequestering agent, a corrosion inhibitor, and a pH adjuster in addition to the above-mentioned components.

The etchant composition of the present invention is a specific example,

Hydrogen peroxide is used as the metal film oxidant, and a fluorine-containing compound; Phosphoric acid; Glycols; And a nitrogen atom-containing compound together with the remaining amount of water.

In particular, the etchant composition may be preferably used for etching a copper-based metal film/molybdenum metal film or a copper-based metal film/titanium metal film. However, the use of the composition is not limited to the double layer.

The hydrogen peroxide is a main component that oxidizes copper, molybdenum, and titanium, and contains 1 to 25% by weight, preferably more than 1 and 10% by weight or less, and more preferably more than 1 and 5% by weight or less, based on the total weight of the composition. It is good to be. When the above-described range is satisfied, a decrease in etching rates of copper, molybdenum, and titanium is prevented, an appropriate amount of etching may be implemented, and an excellent etching profile may be obtained. However, outside the above-described range, the layer to be etched may not be etched, or over-etching may occur, resulting in loss of patterns and loss of functions as a metal wiring.

It is preferable that the components constituting the etchant composition of the present invention have a purity for semiconductor processing.

The present invention also,

a) forming a gate electrode on the substrate;

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

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

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

e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,

Step a), d) or e) comprises forming an electrode by forming a metal film and etching the metal film with the etchant composition of the present invention. It is about.

The array substrate for a liquid crystal display manufactured by the above method includes an electrode having an excellent etching profile, and thus has excellent driving characteristics.

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

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

< Etchant Composition preparation and etching endurance measurement>

Example 1 to 6 and Comparative example 1 to 3.

An etchant composition was prepared by mixing the components shown in Table 1 below in the corresponding content (% by weight).

Thereafter, a single Cu layer was etched with the composition to observe etching endurance.

Etching of a single Cu layer was performed using the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 3 of Table 1 below. During the etching process, the temperature of the etchant composition was set to about 30°C, and etching was performed for 100 seconds. At the time point of 100 and 5000 sheets processed, EPD (End Point Detection, metal etch time) is measured with the naked eye to obtain an etching rage over time, compared to the etch rate at the time of 100 sheets processed, at the time of 5000 sheets processed. The etching endurance, which is the etch rate of, was obtained.

division Hydrogen peroxide Ammonium fluoride Phosphoric acid Triethylene glycol Glycine Deionized water Etch rate (Å/sec) 100 sheets 5000 sheets Etching endurance Example 1 5 2 0.1 5 - Balance 59 55 0.93 Example 2 5 2 0.1 5 One Balance 122 118 0.97 Example 3 3 2 0.1 5 One Balance 115 111 0.97 Example 4 10 2 0.1 5 One Balance 128 123 0.96 Example 5 5 2 0.05 5 One Balance 119 109 0.92 Example 6 5 2 0.5 5 One Balance 133 129 0.97 Comparative Example 1 5 2 - 5 One Balance 110 95 0.86 Comparative Example 2 5 2 0.1 - One Balance 125 35 0.28 Comparative Example 3 5 2 0.1 One One Balance 123 88 0.72

Claims (9)

Based on the total weight of the composition,
1 to 40% by weight of metal film oxidizer;
0.1 to 5% by weight of a fluorinated compound;
0.01 to 10% by weight of phosphoric acid;
0.1 to 10% by weight of glycols; And
As an etchant composition containing the remaining amount of water,
The glycols are polyethylene glycols having a molecular weight of 1000 or less,
The etchant composition is characterized in that the etch rate at the time of 5000 sheets of treatment compared to the etch rate at the time of 100 treatment sheets is 0.9 to 1, etchant composition. The etchant composition according to claim 1, wherein the metal layer oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid and halide. delete The etchant composition of claim 1, further comprising 0.1 to 10% by weight of the nitrogen atom-containing compound. The etchant composition according to claim 4, wherein hydrogen peroxide is included as the metal layer oxidizing agent. The method according to claim 5, wherein hydrogen peroxide is contained in an amount of 1 to 25% by weight as the metal film oxidizer based on the total weight of the composition; Etching liquid composition, characterized in that the nitrogen atom-containing compound is an amino acid. The etchant composition of claim 1, wherein the etchant composition is used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of them. The etchant composition according to claim 7, wherein the multilayer film is a copper-based metal film/molybdenum metal film, a copper-based metal film/titanium-based metal film, or a copper-based metal film/molybdenum-titanium-based alloy film. a) forming a gate electrode on the substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source/drain electrodes on the semiconductor layer; And
e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
The step a), d) or e) comprises forming a metal film, and etching the metal film with the etchant composition of any one of claims 1, 2, and 4 to 8 to form an electrode. A method of manufacturing an array substrate for a liquid crystal display device.