TW201600644A - Etching solution composition for metal layer and manufacturing method of an array substrate for liquid crystal display using the same - Google Patents

Abstract

Disclosed herein is an etching solution composition comprising a metal layer oxidant; a fluorine compound; chelating agents; and remainder of water, wherein the chelating agents comprise specific repeating units and the amount of the repeating units contained in the chelating agents is 0.6 to 2 mmol based on the etching solution composition of 1g; and a manufacturing method of an array substrate for liquid crystal display using the composition.

Description

Etching liquid composition and method for manufacturing array substrate for liquid crystal display using same

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

As flat screen displays such as LCDs, PDPs and OLEDs, in particular TFT-LCDs, have become larger, a single layer of copper or copper alloy has been widely reconsidered, or copper or copper alloys/other metals, alloys of other metals or A plurality of layers of metal oxide are larger than two layers in order to reduce wiring resistance and improve adhesion to the dielectric layer. For example, a copper/molybdenum layer, a copper/titanium layer, or a copper/molybdenum-titanium layer may be formed as a gate line of a TFT-LCD and a source/twist line constituting a data line, and may contribute to an enlarged display screen. Therefore, there is a need to develop a composition having excellent etching characteristics for etching these metal layers including a copper-based layer.

As the etching composition mentioned above, hydrogen peroxide and an amino acid etching liquid, hydrogen peroxide and a phosphoric acid etching liquid, hydrogen peroxide, a polyethylene glycol type etching liquid, or the like are generally used.

As an example, Korean Patent Application Publication No. 10-2011-0031796 discloses an etching solution comprising a water-soluble compound, having: A) a peroxide (H ₂ O ₂ ), B) a persulfate, and C) an amine group. And carboxyl soluble compounds and water.

Korean Patent Application Publication No. 10-2012-0044630 discloses an etching solution for a metal layer containing copper, comprising: hydrogen peroxide, phosphoric acid, a cyclic amine compound, a sulfate, fluoroboric acid, and water.

Korean Patent Application Publication No. 10-2012-0081764 discloses an etching solution comprising: A) ammonium hydroxide, B) hydrogen peroxide, C) a fluorine compound, D) a polyol, and E) water.

However, in the aspect of CD loss, slope (taper), pattern straightness, metal residue, storage stability, and number of sheets to be processed of the metal layer containing the copper base layer, the above-mentioned etching liquid cannot be sufficiently satisfied. The conditions required in the related art.

(previous technical literature) (Patent Literature)

Patent Document 1: Korean Patent Application Publication No. 10-2011-0031796.

Patent Document 2: Korean Patent Application Publication No. 10-2012-0044630.

Patent Document 3: Korean Patent Application Publication No. 10-2012-0081764.

Accordingly, the present invention has been devised to solve the above problems, and an object of the present invention is to provide an etching liquid composition which has excellent work safety, excellent etching rate, and excellent handling of a large number of sheets. Ability; and an array for manufacturing a liquid crystal display using the composition The method of column substrate.

In order to achieve the above object, an aspect of the present invention provides an etching solution composition comprising: a metal layer oxidizing agent, a fluorine compound, a chelating agent, and a remaining amount of water, wherein the chelating agent comprises the following compound of Chemical Formula 1, and In 1 g of the etching liquid composition, the amount of Chemical Formula 1 contained in the chelate compound is from 0.6 mmol to 2 mmol.

Wherein, l, m and n are each independently an integer of 0 to 2, and l, m and n are not all 0; wherein X, Y and Z are each independently O, N or S; wherein A and B Each is independently CH ₂ or C=O.

A method of manufacturing an array substrate for a liquid crystal display, comprising: a) a step of forming a gate on a substrate; b) a step of forming a gate insulator on a substrate including a gate; c) a step of forming a semiconductor layer on the gate insulator; d) a step of forming a source/drain on the semiconductor layer; and e) a step of forming a photo electrode connected to the source/drain; wherein the aforementioned step a), d) or e) comprises forming a metal layer and using The above-described etching liquid composition of any one of the steps of etching the aforementioned metal layer to form an electrode.

According to the present invention, a large number of substrates can be treated by containing various chelating agents other than diol. Moreover, an example of the metal layer etching solution composition containing a copper-based layer of the present invention provides excellent work safety and an economical disposal effect of the etching liquid by containing a low content of hydrogen peroxide.

Further, the method of manufacturing an array substrate for a liquid crystal display using the etching liquid composition of the present invention can be performed by an array substrate for a liquid crystal display An electrode having an excellent etching profile is formed thereon to fabricate an array substrate for a liquid crystal display having excellent driving characteristics.

The invention is described in detail below.

The present invention relates to an etching solution composition comprising: a metal layer oxidizing agent, a fluorine compound, a chelating agent, and a remaining amount of water, wherein the chelating agent comprises the following compound of the chemical formula 1, and the etchant composition is the same as the above 1 g The amount of Chemical Formula 1 contained in the aforementioned chelating agent is from 0.6 mmol to 2 mmol:

Wherein, l, m and n are each independently an integer of 0 to 2, and l, m and n are not all 0; wherein X, Y and Z are each independently O, N or S; wherein A and B Each is independently CH ₂ or C=O.

The number of sheets to be processed for the substrate is increased according to a chelating metal ion such as copper ions present in the etching liquid during etching, which is a chelating agent comprising a compound of Chemical Formula 1 and controlling a repeating unit of n in Chemical Formula 1. obtain.

Therefore, the amount of Chemical Formula 1 contained in the chelating agent is preferably from 0.6 mmol to 2 mmol, and more preferably from 0.8 mmol to 1.5 mmol, per 1 g of the etching liquid composition.

If the number of millimoles of the n repeating unit is less than 0.6, the sheet to be processed The increase in the number is not sufficient. Further, if it exceeds 2, there is a problem that the etching rate is suppressed from increasing due to an increase in viscosity.

Further, the chelating agent containing the compound of Chemical Formula 1 may be one or more selected from the group consisting of Chemical Formula 2 to Chemical Formula 7 below:

Wherein p is an integer of 0 or more; q is an integer of 2 to 3; s is an integer of 2 or more; and R, R ₁ and R ₂ are each independently hydrogen or a C1-C4 aliphatic hydrocarbon.

In the present invention, the metal layer oxidizing agent (A) is a main component for oxidizing the metal layer, and is not particularly limited, but may be selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxides, nitric acid, persulfate, and hydrogen halide. One or a plurality of groups consisting of acids, hydrohalides, and the like.

Refers to metal oxide is a metal oxide, e.g., such as Fe ^3+, Cu ^2+, etc., and it comprises dissociated into Fe ³⁺ in the solution state, Cu ²⁺ and other compounds and the like. Persulfates include ammonium persulfate, alkali metal persulfate, oxone potassium oxychloride, and the like, and hydrohalide salts include chlorates, perchlorates, bromates, perbromates, and analog.

The etching liquid composition may be prepared to contain 1% by weight to 40% by weight of a metal layer oxidizing agent, 0.1% by weight to 5% by weight of a fluorine compound, 0.1% by weight to 10% by weight of a chelating agent containing Chemical Formula 1, and the balance water.

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

The content of the chelating agent containing the compound of Chemical Formula 1 is preferably from 2% by weight to 5% by weight. If the content of the compound chelating agent containing the chemical formula 1 is less than 0.1% by weight, it is difficult to expect to increase the number of sheets to be treated for the substrate. Further, if it exceeds 10% by weight, it is difficult to expect an effect of improvement, and more specifically, it is not preferable because the viscosity of the etching liquid is increased to cause a decrease in the etching rate.

The fluorine compound contained in the etching liquid composition of the present invention is used for removing an etching residue and for etching a titanium-based metal layer.

The fluorine compound may be included in an amount of from 0.1% by weight to 5% by weight, based on the total weight of the composition, preferably from 0.1% by weight to 2% by weight.

The above range is preferable because the etching residue can be prevented and the etching of the glass substrate or the underlying layer is not caused.

However, if it is outside the above range, stains are generated in the substrate due to uneven etching characteristics, an excessive etching rate may damage the lower layer, and etching rate control may become difficult during the step.

Preferably, the fluorine compound may be a compound capable of dissociating into a fluoride ion or a polyatomic fluoride ion.

The compound capable of dissociating into a fluoride ion or a polyatomic fluoride ion may be at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, sodium hydrogen fluoride, and potassium hydrogen fluoride.

The etching liquid composition of the present invention is preferably used for etching a copper-based metal layer, a molybdenum-based metal layer, a titanium-based metal layer or the like.

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

The plurality of layers include, for example, a double layer of a molybdenum-based metal layer/copper-based metal layer, a copper-based metal layer as a lower layer and a molybdenum-based metal layer as an upper layer; a copper-based metal layer/a molybdenum-based metal layer double layer, and a molybdenum metal layer as a lower layer And the copper-based metal layer is an upper layer; a copper-based metal layer/a double layer of a molybdenum-based and a titanium-based alloy layer; and a plurality of layers of more than three layers, the copper-based metal layer and the molybdenum-based metal layer are laminated to each other, such as a molybdenum-based metal layer/ Copper-based metal layer/molybdenum-based metal layer or copper-based metal layer/molybdenum group Metal layer / copper based metal layer.

Further, the plurality of layers include, for example, a double layer of a titanium-based metal layer/a copper-based metal layer, a copper metal layer is a lower layer, and a titanium-based metal layer is an upper layer; a copper-based metal layer/titanium-based metal layer is a double layer, and the titanium metal layer is a lower layer and a copper-based metal layer is an upper layer; and a plurality of layers greater than three layers, the copper-based metal layer and the titanium-based metal layer are laminated to each other, such as a titanium-based metal layer/a copper-based metal layer/a titanium-based metal layer or a copper-based metal layer/ Titanium based metal layer / copper based metal layer.

The inter-layer combination structure of the plurality of layers can be determined by considering the materials constituting the upper layer or the lower layer or the adhesion to the layers.

The copper, molybdenum or titanium alloy layer refers to a metal layer which is mainly composed of copper, molybdenum or titanium and which is produced using an alloy of other different metals depending on the film properties. For example, the molybdenum alloy layer refers to one or a plurality of molybdenum as a main component and containing titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), niobium (Nd), and indium (In). The alloy is produced in layers.

The etching liquid composition of the present invention may further contain one or more selected from the group consisting of a compound containing a nitrogen atom and an acid containing a sulfur (S) atom or a phosphorus (P) atom.

The nitrogen atom-containing compound contained in the etching liquid composition of the present invention functions to enhance the etching rate of the etching liquid composition and to increase the number of sheets to be processed.

As the nitrogen atom-containing compound, a nitrogen atom-containing compound known in the art can be used without limitation, and a compound containing an amine group and a carboxylic acid group in the molecule can be typically used.

The compound containing an amine group and a carboxylic acid group in the molecule may include, for example, An α-amino acid having one carbon atom between a carboxylic acid and an amine group, and is typically a monovalent amino acid such as glycine, glutamic acid, glutamine, isoleucine, Proline, tyrosine, arginine, etc.; and polyvalent amino acids such as iminodiacetic acid, nitrilotriacetic acid, ethylene glycol tetraacetic acid.

The nitrogen atom-containing compound may be used singly or in combination of two or more.

The content of the nitrogen atom-containing compound is from 0.1% by weight to 10% by weight, preferably from 1% by weight to 5% by weight, based on the total weight of the composition.

If the nitrogen atom-containing compound is included in the above range, the etching rate of the etching liquid and the number of sheets to be processed can be increased.

The content of the acid containing sulfur (S) atoms or phosphorus (P) atoms is from 0.01% by weight to 10% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the composition.

When the amount of the acid satisfies the above range, the intended function can be performed because the risk of excessive etching and underlying corrosion of the metal layer caused by an acid containing a sulfur (S) atom or a phosphorus (P) atom can be avoided and does not cause The etching rate of the copper metal layer is lowered due to the acid content being too small.

As the acid containing a sulfur (S) atom or a phosphorus (P) atom, any component known in the art such as sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid or the like can be used without limitation, and phosphoric acid is preferably used. Phosphoric acid promotes hydrogen peroxide etching of copper by supplying hydrogen ions to the etching solution. In addition, it increases the solubility in water by combining phosphate with oxidized copper ions to eliminate residual metal layer residues after etching.

The water used in the present invention means deionized water, which is processed using a semiconductor. Water, and preferably more than 18 MΩ/cm of water is used.

In addition to the above-mentioned components, the etching liquid composition of the present invention may further comprise one or more selected from the group consisting of an etch control agent, a surfactant, a metal ion chelating agent, a corrosion inhibitor, and a pH adjuster.

As a specific embodiment of the etching liquid composition of the present invention, hydrogen peroxide may be used as the metal layer oxidizing agent; and, in addition to the fluorine compound, the chelating agent containing the compound of Chemical Formula 1, and water, may further contain a nitrogen-containing atom. One or more of the group consisting of the compound and the acid of the sulfur (S) atom or the phosphoric acid (P) atom.

Specifically, the etching liquid composition is preferably used for etching a copper-based metal layer, a copper-based metal layer/molybdenum metal layer, or a copper-based metal layer/titanium-based metal layer. However, the application of the composition is not limited to these layers.

Hydrogen peroxide is a main component of copper oxide, molybdenum and titanium, and may be contained in an amount of from 1% by weight to 25% by weight, preferably from 1% by weight to 10% by weight, based on the total weight of the composition. It is preferably from 1% by weight to 5% by weight.

When the amount of hydrogen peroxide falls within the above range, the etching rate of copper, molybdenum, and titanium is prevented from being deteriorated, an appropriate amount of etching can be achieved, and an excellent etching profile can be obtained.

However, if it is outside the above range, etching does not occur or over-etching occurs, and thus pattern loss and loss of function as a metal wiring may occur.

Further, for the nitrogen atom-containing compound and the sulfur (S) atom or the phosphorus (P) atom-containing acid, an amino acid and a phosphoric acid may preferably be used, respectively.

The component constituting the etching liquid composition of the present invention preferably has a purity for semiconductor processing.

Further, the present invention relates to a method of manufacturing an array substrate for a liquid crystal display, comprising: a) a step of forming a gate on a substrate; b) a step of forming a gate insulator on a substrate including a gate; c) a gate a step of forming a semiconductor layer on the insulator; d) a step of forming a source/drain on the semiconductor layer; and e) a step of forming a picture electrode connected to the drain; wherein the aforementioned steps a), d) or e) include The step of forming a metal layer and etching the aforementioned metal layer with the etching liquid composition according to any one of the present invention to form an electrode.

The array substrate for a liquid crystal display comprising an electrode excellent in etching profile produced by the above method according to the present invention has excellent driving characteristics.

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

The present invention will be described in more detail below by means of this embodiment. However, the following examples are intended to explain the present invention in detail, and the scope of the invention is not limited to the following examples. Those skilled in the art can appropriately modify the following embodiments within the scope of the present invention.

(Example)

Examples 1-9 and Comparative Examples 1-3: Preparation of Etching Solution Composition

The etching liquid composition was prepared by mixing these components in the amounts specified in Table 1 below.

Further, the amount of millimolar of the compound of Chemical Formula 1 contained in the chelating agent is referred to as "chelating concentration" with respect to the total weight of the compound. (chelating concentration).

Experimental Example 1: Evaluation of Etching Profile of Etching Solution Composition for Cu/Mo-Ti Bilayer

The Cu/Mo-Ti double layer was etched using the etching liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 3. At the time of etching, etching was performed for 100 seconds with an etching liquid composition having a temperature of about 30 °C. EPD (End Point Detection, Metal Etch Timing) was measured with the naked eye to obtain an etch rate according to time. The profile cross section of the etched Cu/Mo-Ti double layer was examined using SEM (Hitachi Co., Ltd., model S4700), and the results are shown in Table 2 below.

Experimental Example 2: Evaluation of the number of sheets to be processed

A reference test (reference etching) was carried out by using the etching liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 3, and 4000 ppm of copper powder was added to the etching liquid of the reference test and completely dissolved. Thereafter, etching was again performed to carry out a reference test, and the drop ratio of the etching rate was evaluated.

<Evaluation criteria>

○: Excellent (decreased etching rate is less than 10%)

△: good (the rate of decrease in etching rate is 10% to 20%)

×: not good (the etch rate drop ratio is greater than 20%)

Claims (10)

An etchant composition comprising: a metal layer oxidizing agent, a fluorine compound, a chelating agent, and a remaining amount of water; wherein the chelating agent comprises the compound of the following Chemical Formula 1, and the chelating agent is contained in the foregoing etchant composition with respect to 1 g The amount of the chemical formula 1 is from 0.6 mmol to 2 mmol; Wherein l, m and n are each independently an integer of 0 to 2; l, m and n are not all 0; X, Y and Z are each independently O, N or S; and A and B are each independently CH ₂ or C=O. The etching liquid composition according to claim 1, wherein the chelating agent comprising the compound of Chemical Formula 1 is one or more selected from the group consisting of Chemical Formula 2 to Chemical Formula 7 below: [Chemical Formula 4] Wherein p is an integer of 0; q is an integer from 2 to 3; S is an integer of 2 or more; and R, R ₁ and R ₂ are each independently hydrogen or C1-C4 aliphatic hydrocarbons. The etching liquid composition according to claim 1, wherein the metal layer oxidizing agent is selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxides, nitric acid, persulfates, hydrohalic acids, and hydrohalides. One or more species. The etching liquid composition according to claim 1, wherein the first metal layer oxidizing agent is contained in an amount of from 1% by weight to 40% by weight based on the total weight of the foregoing composition; from 0.1% by weight to 5% by weight of the aforementioned fluorine compound; a chelating agent comprising a compound of Chemical Formula 1 in an amount by weight to 10% by weight; The remaining amount of water. The etching liquid composition according to claim 4, further comprising a group selected from the group consisting of 0.1% by weight to 10% by weight of a nitrogen atom-containing compound and 0.01% by weight to 10% by weight of a sulfur atom or a phosphorus atom-containing acid. One or more of them. The etching solution composition according to claim 5, wherein the metal layer oxidizing agent is hydrogen peroxide. The etching liquid composition according to claim 6, wherein the metal layer oxidizing agent is 1% by weight to 25% by weight of hydrogen peroxide with respect to the total weight of the composition; the nitrogen atom-containing compound is an amino acid; And the aforementioned acid containing a sulfur atom or a phosphorus atom is phosphoric acid. The etching liquid composition according to claim 1, wherein the etching liquid composition is used for etching a copper-based metal layer, a molybdenum-based metal layer, a titanium-based metal layer, or a plurality of layers. The etching liquid composition according to claim 8, wherein the plurality of layers are a copper-based metal layer/molybdenum-based metal layer, a copper-based metal layer/titanium-based metal layer, or a copper-based metal layer/molybdenum-titanium-based alloy layer. A method of manufacturing an array substrate for a liquid crystal display, comprising: a) a step of forming a gate on a substrate; b) a step of forming a gate insulator on a substrate including a gate; c) a step of forming a semiconductor layer on the gate insulator; d) a step of forming a source/drain on the semiconductor layer; and e) a step of forming a picture electrode connected to the drain; The step a), d) or e) includes the step of forming a metal layer and etching the metal layer with the etching liquid composition according to any one of claims 1 to 9 to form an electrode.