KR101978389B1 - Etchant composition and manufacturing method of an array substrate for image display device - Google Patents

Abstract

The etchant composition according to the present invention comprises persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Organic acids; Organic acid salts; Sulfamic acid; Glycine; And water, wherein the sulfamic acid is contained in an amount of 0.1 to 6% by weight, and the glycine is contained in an amount of 0.1 to 5% by weight based on 100% by weight of the entire etching composition.
The etchant composition according to the present invention has an advantage that the etching rate of the desired copper film can be maintained for a longer period of time because the etching rate of the etching solution composition is improved compared with that of the conventional etchant.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etchant composition for an image display device,

The present invention relates to an etchant composition capable of etching a copper film and a titanium film, and a method of manufacturing an array substrate for an image display device using the same.

With the development of the information technology (IT) field, the roles of semiconductor integrated circuits (ICs), semiconductor devices and semiconductor devices have become increasingly important in modern society, and they are widely used in various industrial electronic devices. [0002] As electronic devices have become more compact, thinner, lighter, and have higher performance, semiconductor devices to be used require excellent storage capacity and high-speed storage operation. With such high integration of semiconductor devices, it is necessary to form fine patterns of several tens nanometers (nm) or less.

Korean Patent Publication No. 2012-0138290 discloses an etching solution composition and a method for forming a metal wiring and a thin film transistor substrate using the same. The etching solution composition comprises 0.5 to 20 wt% persulfate, 0.01 to 2 wt% 1 to 10% by weight of an inorganic acid, 0.5 to 5% by weight of a cyclic amine compound, 0.1 to 10% by weight of a sulfonic acid, 0.1 to 10% by weight of an organic acid and a salt thereof , And water to make the total weight of the total composition 100 wt%. ≪ Desc / Clms Page number 2 >

However, in the case of the conventional non-conductive metal film etchant composition, as the copper ion is increased in the chemical solution, the taper angle of the metal film becomes larger and the side edge amount decreases, resulting in a lot of deformation in the desired etching shape. Therefore, since the etchant can not be used for a long time and needs to be frequently replaced, there is a problem in that an economic loss is large and a product cost increases. In addition, when the triple-layer etching is performed, the upper titanium film tip is longer than the conventional length, and batch etching is difficult.

Korea Open Patent No. 2012-0138290 (2012.26.)

It is an object of the present invention to provide an etchant composition which is excellent in stability over time and has an effect on the high treatment count because the etch profile is not deformed.

It is also an object of the present invention to provide an etchant composition capable of etching multiple films of a titanium film and a copper film.

It is also an object of the present invention to provide a metal wiring forming method capable of forming uniform wiring and a manufacturing method of an array substrate for an image display apparatus.

To achieve the above object, the etchant composition of the present invention comprises persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Organic acids; Organic acid salts; Sulfamic acid; Glycine; And water, wherein the sulfamic acid is contained in an amount of 0.1 to 6% by weight, and the glycine is contained in an amount of 0.1 to 5% by weight based on 100% by weight of the entire etching composition.

The method for forming a metal wiring of the present invention is characterized by comprising etching the copper film and the titanium film with the etching composition described above.

Further, a manufacturing method of an array substrate for an image display apparatus of the present invention includes the steps of: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming a source and a drain wiring on the semiconductor layer; Forming a copper film and a titanium film on the semiconductor layer and etching the copper film and the titanium film with the etchant composition described above to form source and drain regions, And forming a wiring.

The etchant composition according to the present invention has an advantage that the etching rate of the desired copper film can be maintained for a longer period of time because the etching rate of the etching solution composition is improved compared with that of the conventional etchant.

Further, the method of manufacturing a metal wiring and the method of manufacturing an array substrate for a display device according to the present invention have an advantage that a uniform metal wiring can be manufactured.

1 is a diagram showing a change in a taper angle according to the number of processed sheets.
FIG. 2 is a diagram showing a side etching change according to the number of processes.
FIGS. 3A and 3B are diagrams showing the results of the batch etching test on the triple layer according to the embodiment and the comparative example.

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

When a member is referred to as being " on " another member in the present invention, this includes not only when a member is in contact with another member but also when another member exists between the two members.

Whenever a part is referred to as " including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

< Etchant  Composition>

One aspect of the present invention relates to a process for the preparation of a composition comprising: persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Organic acids; Organic acid salts; Sulfamic acid; Glycine; And water, wherein the sulfamic acid is contained in an amount of 0.1 to 6% by weight based on 100% by weight of the total of the etching solution composition, and the glycine is contained in an amount of 0.1 to 5% by weight.

The etchant composition according to the present invention may further include additives such as an etch control agent, a surfactant, and a pH adjuster in addition to the above-mentioned components insofar as the effect of the present invention is not impaired.

In one embodiment of the present invention, the persulfate is used in an amount of 0.5 to 20% by weight based on 100% by weight of the total of the etchant composition; 0.01 to 2.0% by weight of the fluorine compound; 0.1 to 10% by weight of the inorganic acid; 0.1 to 5% by weight of the cyclic amine compound; 0.1 to 20% by weight of the organic acid; 0.1 to 10% by weight of the organic acid salt; And water balance.

Persulfate

The etchant composition of the present invention comprises persulfate. The persulfate may act as a peroxide forming agent to taper the copper film and the titanium film during etching.

The persulfate may be contained in an amount of 0.5 to 20% by weight, preferably 1 to 18% by weight, more preferably 5 to 15% by weight based on 100% by weight of the total of the etchant composition. In this case, have. If the amount of the persulfate is less than the above range, the etching rate may be somewhat lowered and sufficient etching may not be performed. If the persulfate exceeds the above range, the etching rate may be somewhat too high to control the etching degree. There is a problem that overetching may occur.

In another embodiment of the present invention, the persulfate is selected from potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ). &Lt; / RTI &gt;

Fluorine compound

The etchant composition according to the present invention comprises a fluorine compound. When the etching solution composition according to the present invention contains a fluorine compound, etching of the titanium film is advantageous. Specifically, the fluorine compound is a compound capable of dissociating into fluorine ions or polyatomic fluorine ions in the etchant composition, and is capable of etching the titanium film and removing residues that may be generated by the etching .

In another embodiment of the present invention, the fluorine compound is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, And potassium bifluoride. In addition, the present invention is not limited thereto. In short, the fluorine compound may include, but is not limited to, a mixture of two or more of the above.

The fluorine compound may be contained in an amount of 0.01 to 2.0% by weight, preferably 0.1 to 1.0% by weight based on 100% by weight of the total of the etchant composition, but is not limited thereto. However, when the fluorine compound is included in the above range, the titanium film is etched in a proper amount, and an excellent etching profile can be obtained. When the fluorine compound is contained in a range of the lower limit of the above range, the etching rate of the titanium film is lowered to prevent the residue from being formed, and a desired degree of etching can be achieved. It is preferable that the titanium film is included within the above-mentioned range because it prevents damages to the insulating film such as the silicon film and the substrate such as glass on which the titanium film is laminated other than the titanium film.

Inorganic acid

The etchant composition of the present invention comprises an inorganic acid. The inorganic acid can act as a co-oxidant, and the etching rate can be controlled according to the content of the inorganic acid.

When the inorganic acid is included in the etchant composition, the inorganic acid may react with the copper ions eluted in the copper film etching process, thereby preventing the copper ions from being increased, thereby preventing the etching rate or the etching rate from being reduced There is an advantage to be able to.

The inorganic acid is 0.1 to 10% by weight, preferably 1 to 5% by weight, more preferably 2 to 4% by weight based on 100% by weight of the total of the etchant composition. In this case, There is a possible advantage.

When the amount of the inorganic acid is less than the above range, the etching rate may be lowered to a sufficient extent, and a sufficient etching rate may not be attained. If the amount exceeds the above range, a crack may be formed in the photoresist film used in etching the copper film, Can occur. If the photoresist layer is cracked or the photoresist layer is peeled off, the titanium or copper layer located under the photoresist layer may be excessively etched. Therefore, the inorganic acid may be included in the range of 100 wt% desirable.

The inorganic acid may include, for example, nitric acid, sulfuric acid, phosphoric acid or perchloric acid, alone or in combination of two or more, but is not limited thereto.

Ring Amine  compound

The etchant composition according to the present invention comprises a cyclic amine compound. When the cyclic amine compound is included in the etchant composition, it plays a role of preventing corrosion and can control the etching rate.

The cyclic amine compound may be contained in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight, more preferably 0.5 to 1% by weight based on 100% by weight of the total of the etchant composition. When the amount of the cyclic amine compound is less than the above range, there is a risk that the etching rate of the copper film is increased to some degree, and there is a risk of over-etching. If the above range is exceeded, the etching rate of the copper film may be somewhat lowered and desired etching may not be obtained.

Examples of the cyclic amine compound include aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, and pyrrolidine. Specifically, the cyclic amine compound may be an aminotetrazole compound, and more specifically, may be 5-aminotetrazole, but is not limited thereto.

Organic acids and Organic acid salt

The etchant composition according to the present invention may include organic acids and organic acid salts.

The organic acid and the organic acid salt serve to control the etching rate of the etching solution composition according to the present invention. Specifically, the organic acid may increase the etching rate of the etching composition as the content of the organic acid composition increases, and the organic acid salt may lower the etching rate as the content of the organic acid salt increases in the etching composition.

Although not wishing to be bound by theory, the organic acid salt acts as a chelate to form a complex with the copper ion eluted during the etching of the copper film in the etchant composition, thereby controlling the etching rate of the copper film.

In short, the etchant composition according to the present invention can control the etching rate by adjusting the content of the organic acid and the organic acid salt to an appropriate level.

The organic acid may be contained in an amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 5% by weight based on 100% by weight of the total of the etchant composition. When the organic acid is included in the above range, it exhibits an appropriate etching rate and it is easy to control the taper angle of the copper film.

If the organic acid is contained in the range below the above range, the etching rate may be somewhat lowered and the taper angle of the copper film may be lowered. If the organic acid exceeds the above range, the etching rate may be somewhat accelerated, and the taper angle may become higher than intended.

The organic acid salt may be contained in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight based on 100% by weight of the total of the etchant composition. In this case, .

If the amount of the organic acid salt is less than the above range, it is difficult to control the etching rate of the copper film, and an excessive angle may occur. If the organic acid salt is in the above range, the etching time of the copper film becomes longer as the etching rate of the copper film becomes slower. Since the number of substrates to be treated may decrease, it is preferable that the organic acid and the organic acid salt are contained in the above amounts.

The organic acid may be, for example, a carboxylic acid, a dicarboxylic acid, or a tricarboxylic acid or a tetracarboxylic acid, and more specifically, an acetic acid, a butanoic acid, a citric acid, a formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, wherein the salt is selected from the group consisting of salicylic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, succinic acid, malic acid, or a mixture of two or more thereof, such as tartaric acid, isocitric acid, propenoic acid, imminodiacetic acid, and ethylenediaminetetraacetic acid (EDTA) .

The organic acid salt may include a potassium salt, a sodium salt or an ammonium salt of the organic acids.

Sulfamic acid

The etchant composition of the present invention may contain sulfamic acid as an additive for preventing deterioration over time. The sulfamic acid can serve to maintain the desired taper angle. When the sulfamic acid is included in the etchant composition, copper solubility is improved and the copper ions deposited on the copper deposited film, that is, the copper film, can be easily dissolved in the etching solution, and a larger amount of the substrates There is an advantage to be able to etch.

The sulfamic acid may be contained in an amount of 0.1 to 6% by weight, preferably 1 to 5% by weight, more preferably 2 to 4% by weight based on 100% by weight of the entire etching composition. In this case, have.

If the sulfamic acid is contained in the range below the above range, the function of maintaining the etching shape can not be sufficiently performed, so that the replacement period of the chemical solution, that is, the etching solution may be shortened. If the range is exceeded, There is a problem that control can be difficult.

Glycine

Glycine may be included in the etchant composition to maintain a desired side etch amount. In addition, since glycine has no change with time of the component itself, it can suppress the change of the etchant composition over time when included in the etchant composition, and chelates copper ions eluted in the solution to stabilize the chemical solution Can be performed.

The glycine may be contained in an amount of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight based on 100% by weight of the entire etchant composition. In this case, , There is an advantage that the number of processed wafers increases.

When the glycine is contained in an amount less than the above range, the chelating effect on the copper ions eluted from the copper film may be somewhat reduced, and the stability of the chemical solution may be decreased. When the content exceeds the above range, And the etching time may be somewhat increased in the process. Therefore, it is preferable that the etching time is included within the above range.

water

The etchant composition of the present invention comprises, per 100% by weight of the total, 0.5-20% by weight of the persulfate; 0.1 to 10% by weight of the inorganic acid; 0.1 to 5% by weight of the cyclic amine compound; 0.1 to 20% by weight of the organic acid; 0.1 to 10% by weight of the organic acid salt; 0.1 to 6% by weight of the sulfamic acid; 0.1 to 5% by weight of glycine; And water of the remainder.

The water may be appropriately adjusted in consideration of the content of the etchant composition. Examples of the water include pure water, ultrapure water, deionized water, distilled water, and the like, and it is preferably deionized water. It is more preferable to use deionized water having a resistivity value of 18 M OMEGA.

In yet another embodiment of the present invention, the etchant composition is an etchant composition of a copper film and a titanium film.

The etchant composition according to the present invention comprises persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Organic acids; Organic acid salts; Sulfamic acid; Glycine; And water. The sulfamic acid is contained in an amount of 0.1 to 6% by weight based on 100% by weight of the total of the etchant composition and 0.1 to 5% by weight of the glycine is contained. There is an advantage that the etch profile can not be deformed in the chemical solution, and the etching solution can be etched more than the conventional etchant composition by using the filled chemical solution. In addition, it is possible to batch etch multiple films consisting of titanium / copper / titanium as well as double films consisting of titanium / copper.

In still another embodiment of the present invention, the copper film may be a copper single film or at least one selected from the group consisting of copper and aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten and vanadium. Specifically, in the present invention, the " copper film " may be a copper single film composed only of copper, or may be a copper alloy film composed of a copper alloy.

In still another embodiment of the present invention, the titanium film may be a titanium single film.

In still another embodiment of the present invention, the copper film and the titanium film may be a multiple film in which a copper film and a titanium film are alternately laminated one or more times, but the present invention is not limited thereto.

Specifically, in the present invention, the copper film and the titanium film may include a double metal film in which a copper film / a titanium film is stacked in this order, a titanium film / a copper film, and the like. Also, a multi-metal film in which a copper film and a titanium film are alternately stacked in three or more layers such as a ternary metal film of a copper film / titanium film / copper film, a ternary metal film of a titanium film / copper film / titanium film, a copper film / A copper film / a titanium film / a copper film, and the like. The thickness of the titanium film may be, for example, 100 to 300 angstroms, but is not limited thereto. The thickness of the copper film may be generally 2000 to 7000 angstroms, but is not limited thereto.

&Lt; Method of forming pattern of metal wiring and method of manufacturing array substrate for display device >

Another aspect of the present invention relates to a method of forming a pattern of a metal wiring including etching the copper film and the titanium film with the etching composition described above. Such a metal wiring forming method can be usefully used for forming a thin film transistor array substrate. Such a thin film transistor array substrate can also be used for manufacturing array substrate for various display devices, memory semiconductor display plate, and the like.

Another aspect of the present invention is a method of manufacturing a semiconductor device, comprising: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming a source and a drain wiring on the semiconductor layer; And d) forming a copper film and a titanium film on the semiconductor layer and etching the copper film and the titanium film with the etchant composition as described above to form source and drain regions, And a method of manufacturing an array substrate for an image display device.

According to the method for manufacturing an array substrate of a display device according to the present invention, it is possible to easily form an excellent metal interconnection, that is, a gate interconnection and a source / drain interconnection. Particularly, There is an advantage to be able to.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "% " and " part " representing the content are by weight unless otherwise specified.

Example  1 to 3 and Comparative Example  1 to 4

An etchant composition comprising the components and composition (wt%) of the following Table 1 was prepared.

Persulfate ^{1 )} Fluorine compound ^{2 )} Inorganic acid ^{3 )} Cyclic amine compound ⁴⁾ Organic acid ^{5 )} Organic acid salt ^{6 )} Sulfamic acid ^{7 )} Glycine DI water Example 1 12 0.7 3.3 0.7 2.0 3.0 4.0 0.5 Balance Example 2 12 0.7 3.3 0.7 2.0 3.0 2.0 0.5 Balance Example 3 12 0.7 3.3 0.7 2.0 3.0 4.0 2.5 Balance Comparative Example 1 12 0.7 3.3 0.7 2.0 3.0 0 0.5 Balance Comparative Example 2 12 0.7 3.3 0.7 2.0 3.0 7.0 0.5 Balance Comparative Example 3 12 0.7 3.3 0.7 2.0 3.0 4.0 0 Balance Comparative Example 4 12 0.7 3.3 0.7 2.0 3.0 4.0 5.5 Balance 1) APS: ammonium persulfate (ammonium persulfate)
2) AF: ammonium fluoride
3) HNO ₃
4) ATZ: 5-Aminotetrazole
5) AcOH: acetic acid
6) AA: Ammonium acetate
7) SA: Sulfamic acid

Experimental Example  1: Depends on the number of treatments Taper  Measuring variation of each (T / A)

The etchant compositions according to Examples and Comparative Examples were kept at 25 ° C, and 1000 ppm of copper powder was added per hour, followed by etching test of the gate substrate (Ti / Cu = 200/6000 Å). The total etch time was over etched by doubling at the time of Cu etch, and Etchersms 0.5 generation, glass size processing equipment was used. In this case, spraying was used for the chemical liquid injection, the injection pressure was 0.1 MPa, the exhaust pressure in the ether zone was maintained at 20 Pa, and the taper angle (T / A) according to the number of treatments was shown in Table 2 and FIG.

Number of processing
Cu ion (ppm) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 0 34.5 36.1 33.2 35.3 37.6 1000 35.0 36.5 33.5 38.6 36.5 2000 35.2 36.9 33.3 41.0 39.2 3000 35.1 37.2 34.5 43.6 40.6 4000 35.8 37.5 34.7 46.1 42.8 5000 36.0 37.3 35.0 49.4 45.0 6000 36.4 38.5 35.6 - 47.2 7000 37.0 39.6 35.4 - 49.3 8000 37.6 40.3 36.8 - 51.0 9000 38.5 40.9 37.6 - - 10000 38.7 39.7 37.1 - - 11000 38.2 38.6 36.4 - - 12000 37.0 37.4 34.7 - -

FIG. 1 shows the results of SEM (S-4700, Hitachi) measurement of the degree of change in T / A with respect to the copper concentration. Since it can not be used in the actual line process from the point where it deviates more than a certain level based on the initial T / A value, it is replaced with a new liquid. Referring to FIG. 1 and Table 2, in Examples 1 to 3, when the sulfamic acid was in the proper amount range, the T / A change was smaller at higher copper concentration than that of Comparative Examples 1 and 2. Further, It can be seen that it can be used in process time.

Experimental Example  2: Side according to the number of processing Etching (S / E) Measurement of change

The side etching (S / E) according to the number of treatments was measured in the same manner as in Experimental Example 1, and is shown in Table 3 and FIG.

Number of processing
Cu ion (ppm) Example 1 Example 2 Example 3 Comparative Example 3 Comparative Example 4 0 1.12 1.10 1.15 1.02 1.11 1000 1.14 1.10 1.15 1.01 0.63 2000 1.14 1.09 1.16 1.03 0.20 3000 1.13 1.09 1.16 1.02 - 4000 1.13 1.12 1.18 1.01 - 5000 1.12 1.13 1.18 0.98 - 6000 1.13 1.10 1.19 0.95 - 7000 1.11 1.10 1.19 0.88 - 8000 1.14 1.08 1.16 - - 9000 1.16 1.09 1.15 - - 10000 1.12 1.06 1.14 - - 11000 1.11 1.02 1.12 - - 12000 1.04 0.95 1.07 - -

FIG. 2 shows the results of SEM (S-4700, Hitachi) measurement of the degree of change in S / E with respect to the copper concentration according to the glycine content. As with T / A, it can not be used in the actual line process from the point where it deviates more than a certain level from the initial S / E value. Referring to FIG. 2 and Table 3, in the cases of Examples 1 to 3, when the content of glycine was an appropriate amount, the S / E change was smaller at higher copper concentration than Comparative Examples 3 and 4, Can be maintained.

Experimental Example  3: In the triple layer Batch etching Availability  Test

After the etchant composition (chemical solution) according to Examples and Comparative Examples was maintained at 25 占 폚, an etching test was performed with a triple layer substrate (Ti / Cu / Ti = 200/6000/200 占. The experimental conditions and equipment conditions for the etching test are the same as those of Experimental Example 1, and the results are shown in FIGS. 3A and 3B.

3A and 3B, in the case of Examples 1 to 3, the etching of the Ti film on the Cu film was stabilized so that the length of the Ti residue was 0.1 탆 or less, and in Comparative Examples 1 to 4, the average was 0.15 Mu m. In the case of the actual line process, if it is longer than 0.1 탆, the breakage or short circuit of the pixel electrode deposited in the subsequent process is caused. In the case of the comparative examples 1 to 4, it is impossible to apply it to the triple film batch etchant.

Claims (12)

Persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Organic acids; Organic acid salts; Sulfamic acid; Glycine; And water,
Based on 100% by weight of the total of the etching liquid composition,
The sulfamic acid is contained in an amount of 0.1 to 6% by weight,
Wherein the glycine is contained in an amount of 0.1 to 5 wt%. The method according to claim 1,
Based on 100% by weight of the total of the etchant composition,
0.5-20 wt% of the persulfate;
0.01 to 2.0% by weight of the fluorine compound;
0.1 to 10% by weight of the inorganic acid;
0.1 to 5% by weight of the cyclic amine compound;
0.1 to 20% by weight of the organic acid;
0.1 to 10% by weight of the organic acid salt; And
Wherein the composition is included as a remainder of water. The method according to claim 1,
Wherein the sulfamic acid is contained in an amount of 1 to 5% by weight based on 100% by weight of the total of the etchant composition. The method according to claim 1,
Wherein the glycine is contained in an amount of 0.1 to 3% by weight based on 100% by weight of the total of the etchant composition. The method according to claim 1,
Wherein the persulfate comprises at least one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate. The method according to claim 1,
Wherein the fluorine compound includes at least one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride. delete The method according to claim 1,
Wherein the copper film comprises at least one selected from the group consisting of copper alone or copper and at least one selected from the group consisting of aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten and vanadium. The method according to claim 1,
Wherein the titanium film is a titanium sole film. The method according to claim 1,
Wherein the copper film and the titanium film are multilayers in which a copper film and a titanium film are alternately laminated one or more times. A method for forming a pattern of a metal wiring, comprising etching a copper film and a titanium film with an etchant composition according to any one of claims 1 to 6 and 8 to 10. a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor layer on the gate insulating layer;
d) forming a source and a drain wiring on the semiconductor layer; And
e) forming a pixel electrode connected to the drain wiring,
The step d) includes forming a copper film and a titanium film on the semiconductor layer and etching the copper film and the titanium film with the etchant composition according to any one of claims 1 to 6 and 8 to 10 to form a source And a step of forming a drain wiring.

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