TWI614550B - Manufacturing method of array substrate for liquid crystal display and etching liquid compositions for multi film thereof - Google Patents

Abstract

The invention relates to a method for preparing an array substrate for a liquid crystal display device, and an etching solution composition for a multilayer film. The method includes: a) forming a gate wiring on the substrate; and step b) on a substrate including the gate wiring. Forming a gate insulating layer, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e) forming a connection with the drain Element electrode, wherein step a) or step d) includes a step of forming each electrode by etching a film containing a molybdenum-based metal film or a copper-based metal film, and the molybdenum alloy film is one of niobium or tungsten The above etching solution composition for the above alloy with molybdenum for etching includes: the weight percentage of the total weight of the composition is A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent to 1.0 weight of fluorine compound Percentage; C) 0.1 to 5 weight percent of azole compounds; D) Water-soluble compound with nitrogen atom and carboxyl group in one molecule 0.1 to 5.0 weight percent E) 0.1% to 5.0% by weight of the phosphate compound; F) 0.001% to 5.0% by weight of the polyhydric alcohol surfactant; and G) the remaining amount of water, in addition to the above components, the above etching solution composition Contains no organic or organic acid salts, inorganic acids or inorganic acid salts, or alicyclic amines.

Description

Method for preparing array substrate for liquid crystal display device and etching solution composition for multilayer film [0001]

The invention relates to a method for preparing an array substrate for a liquid crystal display device and an etching solution composition for a multilayer film.

[0002]

As a circuit for driving a semiconductor device and a flat panel display device, a thin film transistor (TFT) is representative. In the process of preparing a thin film transistor, a metal film is usually formed on the upper part of the substrate as a gate and data wiring material. After a photoresist is formed on a selective area of the metal film, the photoresist is used as a mask for etching. The above metal film.

[0003]

Generally, as a gate electrode and a data wiring material, a copper-containing copper film or a copper alloy film having good conductivity and low resistance, and a metal oxide film having excellent surface adhesion with these films are used. In recent years, in order to improve the performance of a thin film transistor, as a metal oxide film, a film containing gallium oxide, indium oxide, zinc oxide, or a mixture thereof has been used.

[0004]

On the other hand, in the Republic of Korea Publication No. 10-2010-0090538, a composition for etching a copper-based metal film is described. The composition includes hydrogen peroxide (H ₂ O ₂ ), an organic acid, a phosphate compound, and the like. . When the copper-molybdenum film is etched by using the above-mentioned etching composition, a linear and conical profile can be formed. However, when the molybdenum-based metal film and copper-based metal film of molybdenum-niobium (Mo-Nb) are etched at one time, The etching rate becomes slow, and there is a problem that the molybdenum-based metal film of molybdenum-niobium (Mo-Nb) cannot be etched or the etching performance such as residues is extremely low. Moreover, in the Republic of Korea Publication No. 10-2010-0035250, a composition containing ammonium sulfate and cyclohexylamine in the presence of hydrogen peroxide and the like is described. When the above composition is used to etch copper / molybdenum-niobium (Mo -Nb) In the case of a molybdenum-based metal film, a sufficient etching rate for a copper film or a molybdenum film cannot be achieved, and the etching characteristics are severely deteriorated.

Prior Art Document Patent Document (Patent Document 1) Republic of Korea Publication No. 10-2010-0090538 (Patent Document 2) Republic of Korea Publication No. 10-2010-0035250

[0005]

The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a method for preparing an array substrate for a liquid crystal display device using an etchant, which can be used for molybdenum-based metals such as molybdenum-niobium (Mo-Nb). The film and the copper-based metal film are etched once.

[0006]

In addition, an object of the present invention is to provide a method capable of increasing the etching speed and the process speed, and avoiding the occurrence of residues, even when a molybdenum-based metal film such as molybdenum-niobium (Mo-Nb) and a copper-based metal film are etched once. And an etching solution composition with a constant side etch (μm) variation in accordance with the copper concentration.

[0007]

In order to achieve the above object, the present invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing the array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, and step b) Forming a gate insulating layer on the substrate of the electrode wiring, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e) The pixel electrode connected to the drain electrode, and the method for manufacturing the above-mentioned array substrate for a liquid crystal display device is characterized in that the step a) or step d) includes: etching a film containing a molybdenum-based metal film or a copper-based metal film, The step of forming each electrode, the molybdenum alloy film is an alloy of one or more of niobium (Nb) or tungsten (W) with molybdenum, and in the above etching solution composition for etching, each component is in the total weight of the composition The weight percentage range is: A) 5.0% by weight to 25.0% by weight of hydrogen peroxide (H ₂ O ₂ ); B) 0.01% by weight to 1.0% by weight of fluorine compounds C) 0.1 to 5 weight percent of azole compounds; D) 0.1 to 5.0 weight percent of water-soluble compounds having nitrogen atoms and carboxyl groups in one molecule; E) 0.1 to 5.0 weight percent of phosphate compounds F) Polyol surfactants from 0.001% to 5.0% by weight; and G) the remaining amount of water, in addition to the above components, the etching solution composition does not contain organic acids or organic acid salts, inorganic acids or inorganic acid salts Or cycloaliphatic amine.

[0008]

The present invention provides an etchant composition of one or more of niobium (Nb) or tungsten (W) with an alloy of molybdenum and a copper-based metal film, wherein the weight percentage of each component in the total weight of the composition is: A) over Hydrogen oxide (H ₂ O ₂ ) 5.0% by weight to 25.0% by weight; B) 0.01% by weight to 1.0% by weight of fluorine compounds; C) 0.1% by weight to 5% by weight of azole compounds; D) Nitrogen in one molecule Atom and carboxyl water-soluble compounds 0.1 to 5.0% by weight; E) 0.1 to 5.0% by weight of phosphate compounds; F) 0.001 to 5.0% by weight of polyol surfactants; and G) Water remaining Amount, in addition to the above-mentioned components, the above-mentioned etchant composition does not contain an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine.

[0009]

According to the etchant composition of the present invention, even when a molybdenum-based metal film such as molybdenum-niobium (Mo-Nb) and a copper-based metal film are etched at one time, the etching speed and the process speed can be increased, and residues can be avoided And maintain a certain amount of change in side etch (μm) with copper concentration.

[0061]

no

[0010]

FIG. 1 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layer metal film using the etchant composition of Example 2 .

FIG. 2 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 4 .

FIG. 3 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 5 .

FIG. 4 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 7 .

FIG. 5 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 9 .

FIG. 6 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 10 .

[0011]

The invention relates to an etchant composition and a method for preparing an array substrate for a liquid crystal display device using the same. The above-mentioned etchant composition is in a double-layer film composed of a copper / molybdenum alloy for forming a thin film transistor array wiring It can etch the upper copper metal film and the molybdenum alloy film of one or more of niobium (Nb) or tungsten (W) with an alloy of molybdenum with excellent etching characteristics.

[0012]

Specifically, the present invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing the array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, step b), and including the gate electrode. A gate insulating layer is formed on the wiring substrate, step c), a semiconductor layer is formed on the gate insulating layer, step d), a source and a drain are formed on the semiconductor layer, and step e) is formed with the drain The electrode element electrode connected to the electrode, the method for manufacturing the above-mentioned array substrate for a liquid crystal display device, wherein the step a) or the step d) includes: by including one or more of niobium (Nb) or tungsten (W) and The step of forming a molybdenum-based metal film or a copper-based metal film of an alloy of molybdenum to form each electrode. The above-mentioned etching solution composition for etching includes: A) hydrogen peroxide (H ₂ O ₂ ); B) Fluorine compounds; C) azole compounds; D) water-soluble compounds with nitrogen and carboxyl groups in one molecule; E) phosphate compounds; F) polyol surfactants; and G) water .

[0013]

In particular, the etchant composition used in the present invention is characterized in that it does not include organic acids or organic acid salts, inorganic acids or inorganic acid salts, or alicyclic amines in addition to the components A) to G) described above. In the past, in order to increase the etching speed of copper or to create an environment favorable for the etching of copper-based metal films, it is necessary to add inorganic acids or inorganic acids such as organic acids or organic acid salts and sulfates in addition to the component D). A cycloaliphatic amine such as a salt, a cyclic amine compound, and the like, and a conventional etching solution composition including an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine was confirmed by testing. This causes a sharp decrease in the etching efficiency of a molybdenum-based metal film, especially a molybdenum-based metal film that is an alloy of molybdenum (Nb) or tungsten (W) with molybdenum. Further, the etching solution composition of the present invention also exhibits a very excellent copper-based metal film etching rate without the above-mentioned organic acid or organic acid salt, inorganic acid or inorganic acid salt, or alicyclic amine. And etching characteristics, it also shows very excellent etching characteristics for molybdenum-based metal films.

[0014]

In the present invention, the copper-based metal film includes copper in the composition of the film, and the copper-based metal film represents pure copper, copper nitride, copper oxide, or copper alloy. The above-mentioned copper alloy represents one selected from the group consisting of pure copper, copper nitride, and copper oxide, and selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), and silver (Ag). , Chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W) An alloy of more than one metal in the group.

[0015]

And, preferably, the above molybdenum alloy film is an alloy of one of niobium (Nb) or tungsten (W) and molybdenum.

[0016]

Hereinafter, the configuration of the present invention will be described in detail.

[0017]

Etching solution composition

[0018]

A) Hydrogen peroxide (H ₂ O ₂ ) contained in the etchant composition of the present invention is an etching of a copper-based metal film including a molybdenum alloy film and a copper metal film formed on the above-mentioned molybdenum alloy film. The main oxidant that has an effect, preferably, the specific gravity of the above A) hydrogen peroxide (H ₂ O ₂ ) in the total weight of the composition is 5.0% by weight to 25.0% by weight. When the content of the above A) hydrogen peroxide (H ₂ O ₂ ) is less than 5.0% by weight, the etching force of the copper-based metal film and the molybdenum alloy film is insufficient, so that sufficient etching cannot be performed; when the above A) hydrogen peroxide (H _When the content of ₂ O ₂ ) exceeds 25.0% by weight, the etching rate as a whole will be accelerated, which will further increase the difficulty of process control, and the thermal stability due to the increase of copper ions will be greatly reduced.

[0019]

The B) fluorine-based compound contained in the etchant composition of the present invention means a compound that decomposes in water to generate fluorine (F) ions. The B) fluorine-based compound is an auxiliary oxidant that affects the etching rate of the molybdenum alloy film, and is used to adjust the etching rate of the molybdenum alloy film.

[0020]

Preferably, the specific gravity of the content of the above-mentioned B) fluorine compound in the total weight of the composition is 0.01% by weight to 1.0% by weight. When the content of the B) fluorine-based compound is less than 0.01% by weight, etching residues may be generated. When the content of the above-mentioned B) fluorine-containing compound exceeds 1.0% by weight, the etching rate of the glass substrate becomes large.

[0021]

The fluorine-based compound is a substance used in the art, but as long as it is a compound that can be decomposed into a fluorine ion or a polyatomic fluorine ion in a solution, there is no particular limitation. Preferably, the fluorine-based compound is selected from the group including hydrogen fluoride (HF ), Sodium fluoride (NaF), ammonium fluoride (NH4F), ammonium fluoborate (NH4BF4), ammonium bifluoride (NH4F ∙ HF), potassium fluoride (KF), potassium hydride (KHF2), aluminum fluoride (AlF3 ) And fluoboric acid (HBF4) in one or two or more groups. In particular, ammonium bifluoride (NH4F · HF) is preferably used.

[0022]

The C) azole compound contained in the etchant composition of the etchant composition of the present invention is used to adjust the etching rate of copper-based metals, reduce the critical dimension loss (CD Loss) of the pattern, and thereby improve the yield in the process. . The specific gravity of the content of the C) azole compound in the total weight of the composition is 0.1 to 5 weight percent. When the content of the above-mentioned C) azole compound is less than 0.1% by weight, the etching rate of copper is too fast, and the critical dimension loss is excessively large. When the content of the above-mentioned C) azole compound exceeds 5 weight percent, the etching rate of copper becomes slower, and the etching rate of the molybdenum alloy film also becomes slower, thereby causing waste of process time and increasing the possibility of residues of molybdenum alloy residues.

[0023]

The above C) azole compounds are not particularly limited if they are used in the art. For example, it is preferable that the azole compound is a azole compound having 1 to 30 carbon atoms. More preferably, it can be used independently or in a mixture selected from the group consisting of triazole compounds, aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds , Pyrrole-based compounds, pyrrolidine-based compounds, pyrroline-based compounds, and the like, one or two or more groups.

[0024]

D) The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the etchant composition of the present invention is used to prevent an autonomous decomposition reaction of hydrogen peroxide water that may occur when the etchant composition is stored, and to prevent Changes in etching characteristics that occur when a large number of substrates are etched. Generally, in the case of an etching solution composition using hydrogen peroxide water, the hydrogen peroxide water undergoes spontaneous decomposition during storage, thereby leading to a short storage period and a risk factor of container explosion. However, in the case where the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is included, the decomposition rate of hydrogen peroxide water is reduced by nearly 10 times, which is beneficial to the extension of the storage period and the stability guarantee. In particular, when a large amount of copper ions in the etchant composition are left in the copper layer, after a passivation film is formed and the oxide is blackened, it is often impossible to perform etching. When this compound is added, Can prevent this phenomenon. Preferably, the content of the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is 0.1% by weight to 5.0% by weight. When the content of the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is less than the above range, a large number of substrates (about 500 sheets) are etched to form a passivation film, and it is difficult to obtain a sufficient process margin. In addition, when the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one of the above D) exceeds the above range, the etching rate of the molybdenum alloy becomes slow, and in the case of a copper-molybdenum film or a copper-molybdenum alloy film, the taper angle becomes small.

[0025]

Preferably, the above D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is selected from the group consisting of alanine, aminobutyric acid, glutamic acid, and glycine , Iminodiacetic acid, nitrilotriacetic acid, and sarcosine in one or two or more groups.

[0026]

The E) phosphate-based compound contained in the etchant composition of the present invention is a component that improves the tapered contour of the pattern. If the above-mentioned E) phosphate-based compound is not contained in the etching solution composition of the present invention, the etching contour becomes unacceptable. Preferably, the specific gravity of the content of the phosphate compound in the total weight of the composition is 0.1% by weight to 5.0% by weight. When the content of the E) phosphate-based compound is less than the above range, the etching contour becomes unacceptable. When the content of the E) phosphate-based compound exceeds the above range, a problem occurs in that the etching rate of the molybdenum alloy film becomes slow.

[0027]

The above E) phosphate-based compound is not particularly limited as long as it is a salt selected from one or two hydrogens in phosphoric acid to be replaced with an alkaline metal or alkaline earth metal. However, preferably, the above E) phosphate-based compound is selected from the group consisting of One or two or more groups of sodium phosphate, potassium phosphate, and ammonium phosphate.

[0028]

The F) polyol-based surfactant contained in the etchant composition of the present invention increases the uniformity of etching by reducing the surface tension. In addition, after the F) polyol-based surfactant etches the copper film, it covers the copper ions dissolved in the etching solution, thereby suppressing the activity of copper ions and the decomposition reaction of hydrogen peroxide. In this way, when the activity of copper ions is reduced, the process can be stably advanced while using the etchant. The specific gravity of the content of the above-mentioned polyol surfactants in the total weight of the composition is 0.001% by weight to 5.0% by weight. When the content of the F) polyol-based surfactant is less than the above range, the etching uniformity is reduced and the decomposition of hydrogen peroxide is accelerated. When the content of the F) polyol-based surfactant exceeds the above range, a large amount of foam will be generated.

[0029]

Preferably, the F) polyhydric alcohol surfactant is selected from the group consisting of glycerol, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. Alcohol (polyethylene glycol) and other groups of one or two or more.

[0030]

Preferably, G) water contained in the copper-molybdenum alloy film etching solution composition of the present invention is contained in the form of a remaining amount to ensure that the total weight of the composition can be 100% by weight. The water is not particularly limited, and deionized water is preferably used. In addition, it is preferable to use deionized water having a specific resistance value of 18 MΩ · cm or more, which indicates the degree to which ions in the water have been removed.

[0031]

Moreover, in addition to the aforementioned components, conventional additives may be added, such as metal ion chelating agents and preservatives. In addition, the aforementioned additives are not limited thereto, and in order to further exert the effects of the present invention, various other additives disclosed in the art may be selected and added.

[0032]

A) Hydrogen peroxide (H ₂ O ₂ ), B) fluorine compounds, C) azole compounds, D) water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule, E) phosphates Compounds, F) polyhydric alcohol surfactants and the like can be prepared by conventionally known methods. Preferably, the etchant composition of the present invention has purity for semiconductor processes.

[0033]

When the etchant composition of the present invention is used to etch a copper-based metal film, it can reflect a tapered contour with excellent etching uniformity and linearity. The etching solution composition of the present invention does not generate residues during etching, and can avoid problems such as electrical short circuits, unsatisfactory wiring, and reduced brightness. Therefore, the etching solution composition of the present invention is very suitable for preparing an array substrate for a liquid crystal display device having a large screen and a high-brightness circuit.

[0034]

The etchant composition of the present invention can etch the gate electrode and gate wiring, and the source / drain and data wiring layers of a liquid crystal display device made of a copper-based metal at one time.

[0035]

/sec的速度蝕刻鉬類金屬膜，以70～120

/sec的速度蝕刻銅類金屬膜。在LGD蝕刻工序中，當蝕刻速度（Etch rate）緩慢時，蝕刻工序時間（Process Time）增加，進而很難確保批量生產性，因此，如何確保上述範圍的蝕刻速度顯得非常重要。In particular, the etching solution composition of the present invention is characterized in that

etch molybdenum-based metal film at a speed of 70 to 120

/ sec. The copper-based metal film is etched. In the LGD etching process, when the etching rate (Etch rate) is slow, the process time increases, which makes it difficult to ensure mass productivity. Therefore, it is very important to ensure the etching rate in the above range.

[0036]

2. Preparation method of array substrate for liquid crystal display device

[0037]

The invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing an array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, and step b) on a substrate including the gate wiring. Forming a gate insulating layer, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e), forming a connection with the drain The pixel electrode, the method for manufacturing the above-mentioned array substrate for a liquid crystal display device, wherein the step a) or step d) includes: etching a film containing a molybdenum-based metal film or a copper-based metal film to form each electrode. Step: In the above etching solution composition used for etching, the weight percentage of each component in the total weight of the composition ranges from: A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent of fluorine compounds ～ 1.0% by weight; C) 0.1% to 5% by weight of azole compounds; D) Water-solubility with nitrogen atom and carboxyl group in one molecule It was 0.1 weight percent to 5.0 weight percent; E) a phosphate-based compound 0.1 weight percent to 5.0 weight percent; F.) Polyhydric alcohol surfactant 0.001 weight percent to 5.0 weight percent; and G) the remaining amount of water.

[0038]

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

[0039]

In addition, the wiring forming method includes:

[0040]

Ⅰ) forming a molybdenum alloy film on the substrate;

[0041]

Ii) a step of forming a copper-based metal film on the upper part of the above molybdenum alloy film;

[0042]

III) a step of selectively retaining a photoreactive substance on the copper-based metal film; and

[0043]

IV) A step of performing one-time etching on the copper-based metal film and the molybdenum alloy film using the etching solution composition of the present invention.

[0044]

In the wiring forming method of the present invention, it is preferable that the photo-reactive substance is a general photoresist substance and can be selectively retained by a normal exposure and development process.

[0045]

Preferably, the molybdenum alloy film is an alloy of one or more of niobium (Nb) or tungsten (W) with molybdenum.

[0046]

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples and comparative examples are merely for illustrating the present invention, and the present invention is not limited thereto, and various modifications and changes can be implemented.

[0047]

Preparation of Etchant Compositions of Examples 1 to 3 and Comparative Examples 1 to 10

[0048]

The etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 10 were prepared according to the compositions shown in Table 1 below.

[0049]

【Table 1】

(Unit: weight percent)

[0050]

Test example: Evaluation of the characteristics of the etching solution composition

[0051]

A molybdenum alloy film is deposited on a glass substrate (100mm × 100mm), a copper film is deposited on the film, and a photoresist having a predetermined pattern is formed on the substrate through a photolithography process. Examples 1 to 1 are used respectively. In the compositions of Example 3 and Comparative Examples 1 to 10, an etching step was performed on the copper-based metal film. In the test, experimental equipment (type: ETCHER (TFT), SEMES) of the spray etching method was used. When the etching process was performed, the temperature of the etching solution composition was set to about 30 ° C, but the appropriate temperature can be determined according to other Process conditions and other factors are changed as needed. The etching time may vary depending on the etching temperature, and is usually performed for about 80 seconds. The properties of the copper-based metal film which was etched in the above-mentioned etching step were examined by a cross-section SEM (Hitachi's product, model S-4700). The results are shown in Table 2 below.

[0052]

【Table 2】

○: Good △: Fair
X: bad
Unetch: Unetched

[0053]

/sec、鉬鈮蝕刻速度（Mo-Nb）15～30

/sec以上。並且，應保持一定的根據銅濃度的側面蝕刻（Side Etch）（μm）變化量。側面蝕刻（Side Etch）是指在蝕刻後測定的光刻膠末端和下部金屬末端之間的距離。當側面蝕刻變化量大時，薄膜電晶體驅動時信號傳遞速度發生變化，進而導致薄膜電晶體-液晶顯示器（TFT-LCD）特性發生變化，因此，較佳地，側面蝕刻變化量應最小化。在本評估中，假設了當側面蝕刻變化量滿足±0.1μm的條件時能夠繼續將蝕刻液組合物用於蝕刻工序，並實施了實驗。In the LCD etching process, when the etching rate (Etch rate) is slow, the process time increases, which makes it difficult to ensure mass productivity. Therefore, the copper etching rate (Cu Etch rate) should be 70 to 120.

/ sec, Mo-Nb etching speed (Mo-Nb) 15 ～ 30

/ sec or more. In addition, a certain amount of change in side etch (μm) according to copper concentration should be maintained. Side Etch refers to the distance between the photoresist end and the lower metal end measured after etching. When the amount of change in the side etching is large, the signal transmission speed changes when the thin film transistor is driven, which causes the characteristics of the thin film transistor-liquid crystal display (TFT-LCD) to change. Therefore, the amount of change in the side etching should preferably be minimized. In this evaluation, it is assumed that the etching solution composition can continue to be used in the etching process when the side etching change amount satisfies the condition of ± 0.1 μm, and experiments were performed.

[0054]

As can be seen from Table 2, the etching solution compositions of the present invention in Examples 1 to 3 all showed good etching characteristics. In addition, it can be seen from FIG. 1 that the copper-based metal film etched with the etchant composition of Example 2 has an excellent etching profile and linearity, and no etching residues remain.

[0055]

In contrast, in Comparative Example 1 in which the hydrogen peroxide content is less than the appropriate content range, the etching rate of copper (Cu) and molybdenum niobium (Mo-Nb) is too slow, showing an unetched phenomenon, which is neutral. In Comparative Example 2 in which the ammonium fluoride content was less than an appropriate content range, the copper etching rate (Cu Etch rate) was at a satisfactory level, but molybdenum niobium (Mo-Nb) was not etched. In Comparative Example 3 in which the content of aminothiazole was larger than the appropriate content range, both copper and molybdenum and niobium showed no etching.

[0056]

/sec的速度提高到120

/sec的速度，有利於銅蝕刻（Cu Etch），但從第2圖中可知，鉬鈮（Mo-Nb）表現出殘留著殘渣未蝕刻（Unetch）的現象，在包含有有機酸的情況下，不利於鉬鈮蝕刻（Mo-Nb Etch）。On the one hand, unlike Example 2, in the case of Comparative Example 4 in which glycolic acid is included in the combination, the copper etching rate (Cu Etch rate) is from 100

/ sec speed increased to 120

The speed per second is good for copper etching (Cu Etch), but from the second figure, it can be seen that molybdenum niobium (Mo-Nb) shows the phenomenon of residual unetching (Unetch), and it contains organic acids. , Is not conducive to molybdenum niobium etching (Mo-Nb Etch).

[0057]

/sec提高到110

/sec，在比較例6中，銅蝕刻速度從100

/sec提高到130

/sec，進而有利於銅蝕刻，但從第3圖中可知，在銅和鉬鈮表面部能夠觀察到侵蝕現象，並表現出殘留著鉬鈮殘渣的未蝕刻（Unetch）現象，由此可知，在包含有硫酸鹽的情況下，將對蝕刻輪廓造成不利影響。And, unlike Example 2, in the case of Comparative Example 5 in which ammonium sulfate was included in the combination, the copper etching rate was from 100

/ sec increased to 110

/ sec, in Comparative Example 6, the copper etching speed is from 100

/ sec increased to 130

/ sec, which is beneficial to copper etching, but from Figure 3, it can be seen that the corrosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and the unetching phenomenon of molybdenum-niobium residues remains, which shows that In the case where sulfate is contained, the etching profile will be adversely affected.

[0058]

/sec下降到90

/sec，而且鉬鈮蝕刻速度從20

/sec顯著下降到5

/sec，從第4圖中可知，鉬鈮表現出了殘留著殘渣的未蝕刻（Unetch）的現象，如比較例8所示，環已胺的濃度增加到4.0%時，鉬鈮未蝕刻（Unetch），由此可知，在包含有環已胺的情況下，不利於鉬鈮的蝕刻。Additionally, different from Example 2, in the case of Comparative Example 7 in which 1.0% cyclohexylamine was included in the combination, the copper etching rate was from 100

/ sec drops to 90

/ sec, and the molybdenum-niobium etch rate is from 20

/ sec drops significantly to 5

/ sec, it can be seen from the fourth figure that molybdenum and niobium show an unetched phenomenon with residue remaining. As shown in Comparative Example 8, when the concentration of cyclohexanamine is increased to 4.0%, molybdenum and niobium are not etched ( Unetch), which shows that, when cyclohexanamine is contained, it is not good for the etching of molybdenum and niobium.

[0059]

Different from Example 2, in Comparative Example 9 containing 1.0% ammonium sulfate and 1.0% cyclohexanamine in the combination, it can be seen from FIG. 5 that the erosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and it shows that The unetched phenomenon of molybdenum and niobium residues remains, and it can be seen that the etching contour will be adversely affected.

[0060]

Furthermore, in the Republic of Korea Publication No. 10-2010-0035250, a composition containing ammonium sulfate and cyclohexylamine in the presence of hydrogen peroxide and the like is described. As in Comparative Example 10, when the above composition is used to etch copper / In the case of molybdenum-niobium (Mo-Nb), it can be seen from FIG. 6 that the erosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and a sufficient etching rate for molybdenum-niobium cannot be achieved, and the etching characteristics are severely deteriorated.

Domestic Deposit Information [Please note according to the order of deposit organization, date, and number]

no

Information on foreign deposits [Please note according to the order of the depositing country, institution, date, and number]

no

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Claims (10)

[Item 1] A method for preparing an array substrate for a liquid crystal display device includes the following steps: a) forming a gate wiring on a substrate, and step b) forming a gate insulating layer on the substrate including the gate wiring, Step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e), forming a picture element connected to the drain Electrode, where
The above step a) or step d) includes: a step of forming each electrode by etching a film containing a molybdenum-based metal film or a copper-based metal film,
The above molybdenum alloy film is an alloy of one or more of niobium or tungsten with molybdenum,
The above-mentioned etching solution composition used for etching includes: the weight percentage of the total weight of the composition is: A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent to 1.0 weight percent of fluorine compounds; C) azole 0.1% to 5% by weight of a class compound; D) 0.1% to 5.0% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule; E) 0.1% to 5.0% by weight of a phosphate compound; F) a polyol 0.001% to 5.0% by weight of surfactants; and G) the remaining amount of water, in addition to the above components, the above-mentioned etching solution composition does not contain organic acids or organic acid salts, inorganic acids or inorganic acid salts or alicyclic amines . [Item 2] The method for manufacturing an array substrate for a liquid crystal display device according to item 1 of the scope of application for a patent, wherein the array substrate for a liquid crystal display device is a thin film transistor array substrate. [Item 3] The method for preparing an array substrate for a liquid crystal display device according to item 1 of the scope of patent application, wherein the etching solution composition used for etching is in a range of 15 to 30.

etch molybdenum-based metal film at a speed of 70 to 120

/ sec. The copper-based metal film is etched. [Item 4] An etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film, including:
The weight percentage of the total weight of the composition is:
A) 5.0% by weight to 25.0% by weight of hydrogen peroxide;
B) 0.01% by weight to 1.0% by weight of the fluorine compound;
C) 0.1 to 5 weight percent of azole compounds;
D) a water-soluble compound having a nitrogen atom and a carboxyl group in a molecule of 0.1 to 5.0% by weight;
E) 0.1% to 5.0% by weight of the phosphate compound;
F) Polyol surfactants from 0.001% by weight to 5.0% by weight; and
G) the amount of water remaining,
In addition to the above components, the above-mentioned etchant composition does not include an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine. [Item 5] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of patent application, wherein

etch molybdenum-based metal film at a speed of 70 to 120

/ sec. The copper-based metal film is etched. [Item 6] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film according to item 4 of the scope of the patent application, wherein the above-mentioned B) fluorine compound is selected from the group consisting of hydrogen fluoride and fluorine One or more selected from the group consisting of sodium chloride, ammonium fluoride, ammonium fluoborate, ammonium hydrogen fluoride, potassium fluoride, potassium fluoride, potassium fluoride, aluminum fluoride, and fluoboric acid. [Item 7] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film as described in item 4 of the scope of patent application, wherein the above-mentioned C) azole compound is selected from the group consisting of triazole Compounds, aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds, pyrrole compounds, pyrrolidine compounds, and pyrroline compounds More than one in the group. [Item 8] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of the patent application, wherein D) above has a nitrogen atom and The carboxyl water-soluble compound is one or more selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, aminotriacetic acid, and sarcosine. [Item 9] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film according to item 4 of the scope of patent application, wherein the above-mentioned E) phosphate compound is selected from the group consisting of sodium phosphate , Potassium phosphate, and ammonium phosphate. [Item 10] The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of the patent application, wherein the above-mentioned F) polyol-based surfactant is selected One or more selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.