KR102137013B1 - Manufacturing method of an array substrate for display device - Google Patents

Abstract

The present invention is based on the total weight of the composition (A) hydrogen peroxide (H ₂ O ₂ ) 5 to 30% by weight, (B) fluorine compound 0.01 to 3% by weight, (C) 5- (alkyl of 1 to 5 carbon atoms)-1H -0.01 to 3% by weight of tetrazole, (D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) 0.05 to 1% by weight of a sulfate compound, (F) 1 to a polyalcohol type surfactant The present invention relates to a method of manufacturing and etching a copper-based metal film etchant composition comprising 5 wt%, and (G) residual water, and an array substrate for a display device using the etchant composition.

Description

Manufacturing method of array substrate for display device {MANUFACTURING METHOD OF AN ARRAY SUBSTRATE FOR DISPLAY DEVICE}

The present invention relates to a method of manufacturing an array substrate for a display device.

The process of forming a metal wire on a substrate in a semiconductor device is usually composed of a metal film forming process by sputtering, photoresist coating, photoresist forming process in an optional area by exposure and development, and etching process. And cleaning processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region by using a photoresist as a mask, and typically, dry etching using plasma or wet etching using an etchant composition is used.

In such semiconductor devices, resistance of metal wiring has recently emerged as a major concern. This is because the increase in panel size and realization of high resolution are the key factors in technology development, especially because resistance is a major factor causing RC signal delay. Therefore, in order to realize the reduction of the RC signal delay, which is essential for the enlargement of the TFT-LCD, development of a material with low resistance is essential. Therefore, chromium (Cr, specific resistance: 12.7 × 10 ^-8 Ωm), molybdenum (Mo, specific resistance: 5 × 10 ^-8 Ωm), aluminum (Al, specific resistance: 2.65 × 10 ^-8 Ωm), which were mainly used in the past, and these The alloy of is difficult to use as a gate and data wiring used in a large TFT LCD.

Under such a background, interest in a copper-based metal film such as a copper film and a copper molybdenum film and an etching solution composition thereof is high as a new low-resistance metal film. However, in the case of an etchant composition for a copper-based metal film, various types are currently used, but the performance required by a user is not satisfied. For example, in Korean Patent Publication No. 10-2010-0090538, certain contents of hydrogen peroxide, organic acid, phosphate compound, water-soluble cyclic amine compound, water-soluble compound having nitrogen atom and carboxyl group in one molecule, fluorine-containing compound, polyalcohol type surfactant , And discloses an etching liquid composition of a copper-based metal film containing water, but has limitations in terms of side etching control and etching rate maintenance according to the number of treatments when etching a thick metal layer (Cu).

Korean Patent Publication No. 10-2010-0090538

The present invention has been devised to solve the above-mentioned problems in the prior art, and can simultaneously etch a copper-based metal film when manufacturing an array substrate for a display device, while controlling side-etch and taper angle when etching a thick metal layer (Cu). It is possible, and an object of the present invention is to provide an etchant composition capable of maintaining an etch rate according to the number of treatments.

In addition, an object of the present invention is to provide a metal film etchant composition having excellent etch profile and straightness, and also preventing defects in staff coverage and occurrence of etch residue.

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 and drain electrodes on the semiconductor layer; And

(e) forming a pixel electrode connected to the drain electrode;

At least one of the steps (a) or (d) includes forming a copper-based metal film on the substrate, and etching the formed copper-based metal film using an etchant composition,

The etchant composition is (A) 5 to 30% by weight of hydrogen peroxide (H ₂ O ₂ ), (B) 0.01 to 3% by weight of fluorine compound, (C) 5-(alkyl having 1 to 5 carbon atoms) based on the total weight of the composition. 1H-tetrazol 0.01 to 3% by weight, (D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) 0.05 to 1% by weight of a sulfate compound, and (F) a polyalcohol surfactant 1 It provides a method for manufacturing an array substrate for a display device, characterized in that it contains from 5% by weight, and (G) the remaining amount of water.

In addition, the present invention,

(A) 5 to 30% by weight of hydrogen peroxide (H ₂ O ₂ ), (B) 0.01 to 3% by weight of fluorine compound, (C) 5-(alkyl of 1 to 5 carbon atoms)-1H-tetrazole based on the total weight of the composition 0.01 to 3% by weight, (D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) 0.05 to 1% by weight of a sulfate compound, (F) 1 to 5% by weight of a polyalcohol type surfactant , And (G) copper-based metal film etchant composition comprising the remaining amount of water.

In addition, the present invention

(a) forming a copper-based metal film on the substrate;

(b) selectively leaving a photoreactive material on the film formed above; And

(c) using the etching solution composition of the present invention to provide an etching method comprising the step of etching the film formed above.

The copper-based metal film etchant composition of the present invention can simultaneously etch the copper-based metal film, but can control the side etch and taper angle when etching the thick film (Cu) metal layer, and can maintain the etch rate according to the number of treatments. In addition, it provides an excellent etching profile and straightness during etching, and effectively prevents defects in step coverage and generation of etching residue.

The present invention,

(A) 5 to 30% by weight of hydrogen peroxide (H ₂ O ₂ ), (B) 0.01 to 3% by weight of fluorine compound, (C) 5-(alkyl of 1 to 5 carbon atoms)-1H-tetrazole based on the total weight of the composition 0.01 to 3% by weight, (D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) 0.05 to 1% by weight of a sulfate compound, (F) 1 to 5% by weight of a polyalcohol type surfactant , And (G) copper-based metal film etchant composition comprising the remaining amount of water.

In the present invention, the copper-based metal film is a single film of copper or copper alloy; Or it may be a multilayer film including at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, and at least one film selected from a copper film and a copper alloy film, wherein the alloy film is a nitride film. Or it may include an oxide film.

For example, the multilayer film may be a double film or a triple film such as a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum alloy film, or a copper/titanium film. The copper/molybdenum film means to include a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper/molybdenum alloy film means to include a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, and copper The alloy/molybdenum alloy film means a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper/titanium film means a titanium layer and a copper layer formed on the titanium layer.

In addition, the molybdenum alloy layer is, for example, one or more metals selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodynium (Nd), and indium (In). And a layer of molybdenum alloy.

In the present invention, the copper-based thick metal film is a metal film having a thickness of at least 5000 mm 2 or more and is different from the thin film. In case of thick film, when etching with existing etching solution, the corrosion rate is slow, so the process time increases. Therefore, it is difficult to apply the existing etchant because it requires a faster corrosion rate (over 150sec/sec) than the existing etchant. In addition, due to the nature of the thick film, if the taper angle is high (above 60° of taper angle), it may be necessary to adjust the taper angle to be low since it may cause step coverage defects during the subsequent process. Since it is formed high, it is difficult to apply it to a thick film.

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

(A) Hydrogen peroxide (H ₂ O ₂ )

The hydrogen peroxide (H ₂ O ₂ ) is a copper comprising a molybdenum layer and a copper molybdenum alloy film comprising a copper layer formed on the molybdenum layer or a molybdenum alloy layer and a copper molybdenum alloy film comprising a copper layer formed on the molybdenum alloy layer It is the main oxidizing agent that affects the etching of the system metal film.

The hydrogen peroxide is included in an amount of 5 to 30% by weight, preferably 15 to 26% by weight, and more preferably 18.0 to 24.0% by weight based on the total weight of the composition. When included below the above-described range, sufficient etching may not be achieved due to insufficient etching power of the copper-based metal film, and when it is included above the above-described range, exothermic stability due to copper ion increase is greatly deteriorated.

(B) Fluorine-containing compound

The fluorine-containing compound refers to a compound capable of dissociating into water to produce fluorine (F) ions. The fluorine compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum-based metal film including the molybdenum alloy film, and controls the etching rate of the molybdenum-based metal film.

The fluorine compound is contained in an amount of 0.01 to 3% by weight, preferably 0.05 to 1% by weight based on the total weight of the composition. When included below the above-mentioned range, the etching rate of the molybdenum-based metal film is slow, and when it is included above the above-mentioned range, the etching performance of the molybdenum-based metal film is improved, but because the etching rate is generally increased, undercut phenomenon or lower layer (n Semiconductor layers such as +a-Si:H and a-Si:G; oxide semiconductor layers such as AxByCzO (wherein A, B, and C are zinc (Zn), titanium (Ti), cadmium (Cd), and gallium, respectively. (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and a metal selected from the group consisting of tantalum (Ta), x, y and z being 0 or more); Etch damage is large.

The fluorine-containing compound is a material known in the art and is not particularly limited as long as it can dissociate into a fluorine ion or a polyatomic fluorine ion in a solution. Typical examples are hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH ₄ F) HF), sodium bifluoride (NaFHF), potassium bifluoride (KFHF), fluoroboric acid (HBF ₄ ), aluminum fluoride (AlF ₃ ), fluoride Calcium (calcium fluoride, CaF ₂ ), hydrofluoric acid (Hydrofluorosilicic Acid, H ₂ SiF ₆ ) and the like. These may be used alone or in combination of two or more. In particular, ammonium bifluoride (NH ₄ F·HF) can be preferably used.

(C) 5-(alkyl having 1 to 5 carbon atoms)- 1H-tetrazole

The 5-(alkyl having 1 to 5 carbons)-1H-tetrazole controls the etching rate of the copper-based metal film and reduces the CD loss of the pattern to increase the process margin.

The 5-(alkyl having 1 to 5 carbons)-1H-tetrazole is included in an amount of 0.01 to 3% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 1% based on the total weight of the composition. 1.5% by weight. When included below the above-mentioned range, the Etch Profile fluctuation according to over-etching and the number of treatments is large. If it exceeds the above-mentioned range, there may be a process time loss because the etching rate of copper is too slow.

The 5-(alkyl having 1 to 5 carbon atoms)-1H-tetrazole is 5-methyl-1H-tetrazole, 5-ethyl-1H-tetrazole, 5-propyl-1H-tetrazole, 5-butyl-1H- Tetrazole, and the like, and 5-methyl-1H-tetrazole is particularly preferable.

(D) Water-soluble compound having nitrogen atom and carboxyl group in one molecule

The water-soluble compound having a nitrogen atom and a carboxyl group in the molecule prevents the self-decomposition reaction of hydrogen peroxide water that may occur during storage of the etchant composition and prevents etching characteristics from changing when a large number of substrates are etched. In general, in the case of an etchant composition using hydrogen peroxide water, the hydrogen peroxide water self-decomposes during storage, and the storage period is not long and there is a risk that the container may explode. However, when a water-soluble compound having a nitrogen atom and a carboxyl group is contained in one molecule, the decomposition rate of hydrogen peroxide water is reduced by nearly 10 times, which is advantageous for securing storage period and stability. Particularly, in the case of a copper layer, when a large amount of copper ions remain in the etchant composition, a passivation film is formed, and it is often oxidized to black, so that it can no longer be etched, but when this compound is added, this phenomenon can be prevented. .

The content of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule is included in 0.5 to 5% by weight, preferably 1.0 to 3% by weight. When included below the above-described range, after a large amount of substrate (about 500 sheets) is etched, a passivation film is formed, making it difficult to obtain a sufficient process margin. When it exceeds the above-mentioned range, the etching rate of molybdenum or molybdenum alloy is Since it is slow, in the case of a copper molybdenum film or a copper molybdenum alloy film, a problem of residue of the molybdenum or molybdenum alloy film may occur.

The water-soluble compound having a nitrogen atom and a carboxyl group in the molecule includes alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, and nitrotriacetic acid. acid), and sarcosine, and the like. These may be used alone or in combination of two or more. In particular, iminodiacetic acid may be most preferably used among these components.

(E) Sulfate compound

The sulfate is a component that increases the etching rate of the copper film by controlling the oxidation potential of the Cu surface. If the sulfate compound is not present in the etching solution composition of the present invention, the etching rate may be very low, resulting in a poor etching profile.

The content of the sulfate compound is included in 0.05 to 1.0% by weight relative to the total weight of the composition, particularly preferably 0.1 to 0.5% by weight. When included below the above-mentioned range, the etching rate is very low, which may result in poor etching profiles and loss of process time. When it is included beyond the above-mentioned range, the etching rate of the copper or copper alloy film becomes too fast or the taper angle becomes too high. It is vulnerable to poor step coverage, making it difficult to apply thick films.

Examples of the sulfate include ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and lithium sulfate.

(F) Polyhydric alcohol type surfactant

The polyhydric alcohol-type surfactant serves to increase the uniformity of etching by lowering the surface tension. In addition, the polyhydric alcohol-type surfactant suppresses the decomposition reaction of hydrogen peroxide by suppressing the activity of copper ions by surrounding copper ions dissolved in the etchant after etching the copper film. When the activity of copper ions is lowered in this way, the process can be stably performed while using the etching solution.

The polyalcohol-type surfactant is contained in 1 to 5% by weight based on the total weight of the composition, preferably 1.5 to 3% by weight. When included below the above-mentioned range, there may be a problem that etching uniformity is deteriorated and decomposition of hydrogen peroxide is accelerated, and if it exceeds the above-described range, a lot of bubbles are generated.

Examples of the polyalcohol-type surfactant include glycerol, triethylene glycol, and polyethylene glycol, and triethylene glycol is the most preferable.

(E) water

The water contained in the etchant composition of the present invention contains the remaining amount so that the total weight of the composition is 100% by weight. Water in the etching solution composition of the present invention serves to dilute the etching solution composition. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is more preferable to use deionized water having a specific resistance value of 18 MPa·cm or more, which shows the degree of ion removal in water.

Hydrogen peroxide (H ₂ O ₂ ), a fluorine-containing compound, an azole compound, a compound of Formula 1, and a residual amount of water used in the present invention are preferably used in a purity that can be used for semiconductor processing. , Industrial grade can be used by purification according to methods commonly known in the art.

In addition, a conventional additive may be further added to the etchant composition according to the present invention in addition to the components described above. That is, according to a preferred embodiment of the present invention, the etchant composition may further include any one or more additives selected from surfactants, metal ion blockers and corrosion inhibitors.

The surfactant acts to decrease the surface tension and increase the uniformity of etching. As such a surfactant, a surfactant capable of withstanding an etchant and having a compatible form is preferable. Examples include any anionic, cationic, zwitterionic or nonionic surfactants, and the like. Further, a fluorine-based surfactant can be used as the surfactant.

The additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.

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 and drain electrodes on the semiconductor layer; And

(e) forming a pixel electrode connected to the drain electrode;

At least one of the steps (a) or (d) includes forming a copper-based metal film on the substrate, and etching the formed copper-based metal film using an etchant composition,

The etchant composition is (A) 5 to 30% by weight of hydrogen peroxide (H ₂ O ₂ ), (B) 0.01 to 3% by weight of fluorine compound, (C) 5-(alkyl having 1 to 5 carbon atoms) based on the total weight of the composition. 1H-tetrazol 0.01 to 3% by weight, (D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) 0.05 to 1% by weight of a sulfate compound, and (F) a polyalcohol surfactant 1 It relates to a method for manufacturing an array substrate for a display device, characterized in that it contains from 5% by weight, and (G) the remaining amount of water.

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

The semiconductor layer may be formed of n+a-Si:H, a-Si:G, or an oxide semiconductor such as AxByCzO (wherein A, B and C are zinc (Zn) and titanium, respectively). A metal selected from the group consisting of (Ti), cadmium (Cd), gallium (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum (Ta), x, y And z is 0 or more).

The process of each step in the method of manufacturing the array substrate may be performed by methods known in the art.

In the above, the copper-based metal film is the same as described above.

In addition, the present invention

(a) forming a copper-based metal film on the substrate;

(b) selectively leaving a photoreactive material on the film formed above; And

(c) using the etchant composition of the present invention to etch the film comprising the step of etching the formed film.

In the above, the copper-based metal film is the same as described above.

The process of each step of the etching method can be performed by methods known in the art.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples and may be variously modified and changed.

Examples 1 to 9 and Comparative Examples 1 to 5: Preparation of etching solution composition

According to the composition shown in Table 1, an etchant composition 180 kg was prepared.

division H ₂ O ₂ ABF 5-MTZ IDA AS NHP TEG 5-ATZ water Example 1 18 1.0 0.05 1.0 0.1 - 1.5 - Balance Example 2 20 0.5 0.10 1.7 0.2 - 2.0 - Balance Example 3 22 0.1 0.15 2.3 0.3 - 2.5 - Balance Example 4 24 0.05 0.20 3.0 0.5 - 3.0 - Balance Example 5 15 0.1 0.05 2.0 0.5 - 2.0 - Balance Example 6 5 0.5 0.05 2.0 0.5 - 2.0 - Balance Example 7 20 0.1 0.01 2.0 0.5 - 2.0 - Balance Example 8 23 0.1 1.5 2.0 0.5 - 2.0 - Balance Example 9 23 0.1 2 2.0 0.5 - 2.0 - Balance Comparative Example 1 22 0.1 - 2.3 0.3 - 2.5 - Balance Comparative Example 2 22 0.1 0.15 2.3 - - 2.5 - Balance Comparative Example 3 22 0.1 - 2.3 0.3 - 2.5 0.15 Balance Comparative Example 4 22 0.1 - 2.3 0.3 - 2.5 0.50 Balance Comparative Example 5 22 0.1 0.15 2.3 - 0.3 2.5 - Balance

(Unit:% by weight)

ABF: ammonium bifluoride; 5-MTZ: 5-methyltetrazole; AS: ammonium sulfate; TEG: triethyleneglycol; 5-ATZ: 5-aminotetrazole; IDA: iminodiacetic acid; NHP: Sodium Phosphate [Na ₃ HPO ₄ ]

Test example: Etching liquid characteristic evaluation

The etching process was performed using the etching solution compositions of Examples 1 to 9 and Comparative Examples 1 to 5, respectively. Experimental equipment of the spray-type etching method (model name: ETCHER (TFT), SEMES) was used, and the temperature of the etchant composition during the etching process was about 33°C. The etching time may vary depending on the etching temperature, but was performed in about 50 to 80 seconds as is normally performed in the LCD etching process. The profile of the copper-based metal film etched in the etching process was examined using a cross-section SEM (Hitachi, model S-4700), and the results are shown in Table 2 below. In the etching process, a substrate on which a metal film of Cu/Mo-Ti 5000/100Å was deposited was used.

Side Etch (µm) change amount according to Cu concentration was measured. Taper Angle is the slope of the Cu slope and Side Etch is the distance between the photoresist end and the bottom metal end measured after etching. When the amount of side etch is changed, the signal transmission speed is changed during TFT driving, and staining may occur, so it is desirable to minimize the amount of side etch variation. In this evaluation, it was determined that the etchant composition can be continuously used in the etching process when a condition in which the side etch change amount is ±0.1 μm and a taper angle of 40 to 60° is satisfied, and then an experiment is conducted. The amount of change in side etch was determined by measuring the amount of change that decreases or increases at about 0.5 μm on one side using SEM.

division Etch Profile Etch straightness Side etch
Change amount (㎛) Taper angle
(˚) Example 1 ○ ○ 0.08 43~48 Example 2 ○ ○ 0.05 47~53 Example 3 ○ ○ 0.03 48~55 Example 4 ○ ○ 0.05 50~58 Example 5 ○ ○ 0.05 48~55 Example 6 ○ ○ 0.09 40-45 Example 7 ○ ○ 0.09 50~58 Example 8 ○ ○ 0.06 45~55 Example 9 ○ ○ 0.09 42~47 Comparative Example 1 X X 0.8 20~30 Comparative Example 2 Unetch Unetch - - Comparative Example 3 ○ ○ 0.5 50-65 Comparative Example 4 △ △ 0.1 45~60 Comparative Example 5 ○ ○ 0.15 60~80

(Note) ○: Good, △: Normal, Х: Bad, Unetch: Not etchable

As shown in Table 2, the etchant compositions of Examples 1 to 4 of the present invention had excellent etch profiles and straightness, and no Mo and Ti residues were generated. In addition, the side etch change amount was also in the range of ±0.1 μm, and the taper angle was also satisfied with the condition of 40 to 60°.

On the other hand, in Comparative Example 1, which does not include 5-MTZ, it was found that the etching profile was very fast and the etching profile was very poor. The amount of change in side etch was also very large, and the taper angle was 30 degrees or less. In the case of Comparative Example 2 without sulfate, the etching rate of the copper film was very slow, resulting in process unetch. In the case of Comparative Example 3 including 5-ATZ instead of 5-MTZ, the etching profile was excellent, but the side-etch variation was very large, and the taper angle was more than 60 degrees. In contrast, in the case of Comparative Example 4 in which the 5-ATZ content was increased, the side etch change amount and taper angle were satisfied, but the etching profile was poor due to the slow etching rate of the copper film. In the case of Comparative Example 5 containing phosphate instead of sulfate, the etching profile and the etch straightness were good, but the side etch variation was large and the taper angle was formed high.

Claims (14)

(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 and drain electrodes on the semiconductor layer; And
(e) forming a pixel electrode connected to the drain electrode;
At least one of the steps (a) or (d) includes forming a copper-based metal film on the substrate, and etching the formed copper-based metal film using an etchant composition,
The etchant composition includes (A) hydrogen peroxide (H ₂ O ₂ ), (B) a fluorine compound, (C)5-(alkyl having 1 to 5 carbon atoms)- 1H-tetrazole, and (D) nitrogen atoms and carboxyl groups in one molecule. It includes a water-soluble compound having, (E) a sulfate compound, (F) a polyalcohol type surfactant, and (G) water,
The (C)5-(alkyl having 1 to 5 carbon atoms)-1H-tetrazole is contained in an amount of 0.01 to 3% by weight based on the total weight of the composition,
The (C)5-(alkyl having 1 to 5 carbon atoms)- 1H-tetrazole is 5-methyl-1H-tetrazole, 5-ethyl-1H-tetrazole, 5-propyl-1H-tetrazole and 5-butyl -A method for manufacturing an array substrate for a display device comprising at least one member selected from the group consisting of 1H-tetrazole. The method according to claim 1,
The (A) hydrogen peroxide (H ₂ O ₂ ) The method of manufacturing an array substrate for a display device, characterized in that it comprises 5 to 30% by weight relative to the total weight of the composition. delete The method according to claim 1,
The manufacturing method of the array substrate for a display device, characterized in that the array substrate for a display device is a thin film transistor (TFT) array substrate. (A) Hydrogen peroxide (H ₂ O ₂ ), (B) fluorine compound, (C)5-(alkyl having 1 to 5 carbon atoms)- 1H-tetrazole, (D) water-soluble compound having nitrogen atom and carboxyl group in one molecule , (E) a sulfate compound, (F) a polyalcohol type surfactant, and (G) water,
The (C)5-(alkyl having 1 to 5 carbon atoms)-1H-tetrazole is contained in an amount of 0.01 to 3% by weight based on the total weight of the composition,
The (C)5-(alkyl having 1 to 5 carbon atoms)-1H-tetrazole is 5-methyl-1H-tetrazole, 5-ethyl-1H-tetrazole, 5-propyl-1H-tetrazole and 5-butyl -Copper-based metal film etchant composition comprising at least one member selected from the group consisting of 1H-tetrazole. The method according to claim 5,
The (A) hydrogen peroxide (H ₂ O ₂ ) The copper-based metal film etchant composition characterized in that it comprises 5 to 30% by weight relative to the total weight of the composition. delete The method according to claim 5,
The (B) a fluorine compound is hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), sodium fluoride (NaF), potassium fluoride (KF), medium heat screen ammonium (NH ₄ F · HF), medium heat sodium (NaF · HF ) And potassium difluoride (KF·HF), boric acid (HBF ₄ ), aluminum fluoride (AlF ₃ ), calcium fluoride (CaF ₂ ), and hydrofluoric acid (H ₂ SiF ₆ ) 1 A copper-based metal film etchant composition comprising at least a species. The method according to claim 5,
The water-soluble compound having a nitrogen atom and a carboxyl group in the molecule (D) is alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid (nitrilotriacetic acid), and a copper-based metal film etchant composition comprising at least one selected from the group consisting of sarcosine (sarcosine). The method according to claim 5,
The (E) sulfate compound is a copper-based metal film etchant composition, characterized in that one or more selected from the group consisting of ammonium sulfate, ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and lithium sulfate. The method according to claim 5,
The (F) polyalcohol-type surfactant is a copper-based metal film etchant, characterized in that it comprises one or more selected from the group consisting of glycerol (glycerol), triethylene glycol (triethylene glycol) and polyethylene glycol (polyethylene glycol) Composition. The method according to claim 5,
The etchant composition is a copper-based metal film etchant composition, characterized in that it further comprises at least one additive selected from surfactants, metal ion blockers and corrosion inhibitors. The method according to claim 5,
The copper-based metal film is a single film of copper or copper alloy; or
A copper-based metal film etchant composition comprising a multi-layered film comprising at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, and at least one film selected from a copper film and a copper alloy film. (a) forming a copper-based metal film on the substrate;
(b) selectively leaving a photoreactive material on the copper-based metal film formed above; And
(C) etching method comprising the step of etching the copper-based metal film formed above using the etching solution composition of claim 5.