KR20130025614A - An etching solution composition for metal layer containing copper/metal oxide layer containing gallium - Google Patents

Abstract

PURPOSE: An etching composition is provided to uniformly etch a copper-based metal film and a gallium-containing metal oxide film and to prevent the formation of an under cut on the gallium-containing metal oxide film. CONSTITUTION: An etching composition comprises 5-20 weight% of a persulphate salt, 1-15 weight% of an inorganic acid, 0.3-5 weight% of a cyclic amine compound, and residual water. The persulfate salt is one or more selected from ammonium persulfate, sodium persulfate, and potassium persulfate. The inorganic acid is one or more selected from nitric acid, sulfuric acid, phosphoric acid, and perchloric acid. A manufacturing method of a thin film transistor comprises a step of forming patterns by simultaneously etching a copper-based metal film and a gallium-containing metal oxide film.

Description

Etching liquid composition of copper-based metal film / gallium-containing metal oxide film {AN ETCHING SOLUTION COMPOSITION FOR METAL LAYER CONTAINING COPPER / METAL OXIDE LAYER CONTAINING GALLIUM}

The present invention relates to an etching liquid composition of a copper-based metal film / gallium-containing metal oxide film capable of collectively wet etching a copper-based metal film and a gallium-containing metal oxide film.

Typical electronic circuits for driving semiconductor devices and flat panel displays are thin film transistors (TFTs). The manufacturing process of the TFT generally consists of forming a metal film as a gate and data wiring material on a substrate, forming a photoresist in an optional region of the metal film, and then etching the upper metal film using the photoresist as a mask.

Usually, as the gate and data wiring materials, a copper single film or a copper alloy film containing copper having good electrical conductivity and low resistance, and a metal oxide film excellent in interfacial adhesion with these films are used. In recent years, a film containing indium oxide, zinc oxide or a mixture thereof with gallium oxide has been used as a metal oxide film for improving the performance of TFTs. However, this metal oxide film can increase the operation speed of the TFT due to its high charge mobility, but has a disadvantage in that processing, in particular, etching is difficult.

In addition, although one mask including a desired pattern is used to etch one metal film, recently, at least two or more metal films are etched using one mask to minimize the use of expensive masks and simplify the process. do. However, even if a single mask is used, since the etching process is performed in different ways when the properties of the metal film are different from each other, such as a copper single film or a copper alloy film and a metal oxide film, it is difficult to substantially reduce the number of processes.

The present invention relates to an etching liquid of a copper-based metal film / gallium-containing metal oxide film capable of quick and uniform batch wet etching of a copper-based metal film and a metal oxide film containing indium oxide, zinc oxide or a mixture thereof together with gallium or gallium oxide. It is an object to provide a composition.

1. An etching solution composition of a copper-based metal film / gallium-containing metal oxide film, comprising 5 to 20% by weight of persulfate, 1 to 15% by weight of an inorganic acid, 0.3 to 5% by weight of a cyclic amine compound, and a residual amount of water.

2. The above 1, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate, copper-based metal film / gallium-containing metal oxide film etching liquid composition.

3. In the above 1, the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid, the etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

4. In the above 1, the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine An etching liquid composition of a copper-based metal film / gallium-containing metal oxide film, which is at least one selected from the group consisting of a compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound and a pyrroline compound.

5. according to the above 1, wherein the fluorine compound further comprises 0.01 to 2% by weight, the etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

6. In the above 5, the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium fluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, lithium fluoride And at least one selected from the group consisting of calcium fluoride, the etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

7. according to the above 1, further comprising 0.1 to 15% by weight of an organic acid, a salt thereof or a mixture thereof, the copper-based metal film / gallium-containing metal oxide film etching liquid composition.

8. In the above 7, the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, iso citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, An etching liquid composition of a copper-based metal film / gallium-containing metal oxide film, which is at least one member selected from the group consisting of sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and propene acid.

9. In the above 7, wherein the salt is potassium salt, sodium salt or ammonium salt, copper-based metal film / gallium-containing metal oxide film etching liquid composition.

10. In the above 1, further comprising 0.1 to 10% by weight of one or more selected from the group consisting of nitrates, sulfates and perchlorates, etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

11. The above 1, wherein the chelating agent further comprises 0.01 to 3% by weight, the etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

12. In the above 1, the copper-based metal film is a copper single layer containing one or more from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or etching liquid composition of a copper-type metal film / gallium containing metal oxide film which is these laminated films.

13. In the above 1, the gallium-containing metal oxide film is a film containing gallium oxide, indium oxide, zinc oxide or a mixture thereof, the etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.

14. Method of manufacturing a thin film transistor comprising the step of forming a pattern by etching the copper-based metal film and gallium-containing metal oxide film in a batch as the etching liquid composition of any one of 1 to 13.

The etchant composition of the present invention can uniformly wet-etch a copper-based metal film and a gallium-containing metal oxide film at a high etching rate, thereby simplifying an etching process and improving productivity.

In addition, the etching solution composition of the present invention can prevent the undercut formed on the gallium-containing metal oxide film.

In addition, the etchant composition of the present invention does not require expensive equipment during etching and does not damage equipment as well, which is advantageous in terms of large area and thus has an economical advantage.

The present invention relates to an etching liquid composition of a copper-based metal film / gallium-containing metal oxide film capable of collectively wet etching a copper-based metal film and a gallium-containing metal oxide film.

Hereinafter, the present invention will be described in detail.

In the present invention, the 'copper-based metal film / gallium-containing metal oxide film' includes a double film laminated in the order of a copper-based metal film / gallium-containing metal oxide film, and a double film laminated in the order of a gallium-containing metal oxide film / copper-based metal film. do. Further, a multi-metal film in which a copper-based metal film and a gallium-containing metal oxide film are alternately stacked in three or more layers, such as a triple film of a copper-based metal film / gallium-containing metal oxide film / copper-based metal film and a gallium-containing metal oxide film / copper And a triple film of a metal-based metal film / gallium-containing metal oxide film, a multilayer film of a copper-based metal film / gallium-containing metal oxide film / copper-based metal film / gallium-containing metal oxide film / copper-based metal film, and the like. At this time, the thickness of a copper type metal film and a gallium containing metal oxide film is not specifically limited.

In addition, in the present invention, the copper-based metal film is a film containing copper in the constituents of the film, and may be a copper single film composed of one or more selected from the group consisting of pure copper, nitrides thereof, and oxides thereof. In addition, at least one selected from the group consisting of pure copper, nitrides thereof and oxides thereof, aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) It may be a copper alloy film composed of a copper alloy containing one or more, such as a copper alloy film composed of copper and manganese or a copper alloy film composed of copper, magnesium and aluminum. In addition, the copper-based metal film may be a laminated film of a copper single film and a copper alloy film. Hereinafter, a copper metal film is represented by Cu-X.

In the present invention, the 'gallium-containing metal oxide film' is a metal including gallium (Ga) or gallium oxide (Ga ₂ O ₃ ), including indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or a mixture thereof. It is an oxide film. In general, Ga-YO (Y may be represented by In, Zn, or In-Zn).

The etchant composition of the copper-based metal film / gallium-containing metal oxide film of the present invention is characterized by containing persulfate, inorganic acid, cyclic amine compound, and water.

More specifically, 5 to 20% by weight of persulfate, 1 to 15% by weight of inorganic acid, 0.3 to 5% by weight of cyclic amine compound, and balance water.

Persulfate is a main oxidizing agent for etching Cu-X and Ga-YO films. Specific examples thereof include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), potassium persulfate (K ₂ S ₂ O ₈ ), and the like. It can mix and use species.

Persulfate is preferably included in 5 to 20% by weight, more preferably 7 to 12% by weight in 100% by weight of the total etching solution composition. In this content range, the Cu-X film and the Ga-Y-O film are etched in an appropriate amount, and an excellent etching profile can be obtained. If the content is less than 5% by weight, the Cu-X film and the Ga-Y-O film may not be etched or the etching rate is slow, and if the content is more than 20% by weight, the etching rate is faster overall, it may be difficult to control the process.

The inorganic acid is an auxiliary oxidant component for etching the Cu-X film and the Ga-Y-O film. Specific examples include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like, which may be used alone or in combination of two or more thereof.

The inorganic acid may be included in an amount of 1 to 15% by weight, and preferably 2 to 10% by weight in 100% by weight of the etching liquid composition. In this content range, the Cu-X film and the Ga-Y-O film are etched in an appropriate amount, and the etching profile is also excellent. If the content is less than 1% by weight, the etching rate may be lowered, resulting in poor etching profiles and residues. If the content is more than 15% by weight, overetching may occur and cracks may occur in the photoresist. The etchant composition may penetrate and short the wiring.

The cyclic amine compound is a component that forms an etching profile during etching of the Cu-X film and the Ga-Y-O film. Specific examples thereof include 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine compound, pyrimidine compound, A roll type compound, a pyrrolidine type compound, a pyrroline type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The cyclic amine compound may be included in 0.3 to 5% by weight in the total 100% by weight of the etchant composition, preferably 0.5 to 3% by weight. In this content range, an appropriate etching rate and taper angle of the copper-based metal film may be formed, and the amount of side etching may be adjusted. If the content is less than 0.5% by weight, it is difficult to sufficiently control the etching rate of the Cu-X film, and overetching may occur. If the content is more than 5% by weight, the etching speed of the Cu-X film is lowered, resulting in a longer etching time and lowering productivity. Can be.

The etchant composition may further include a fluorine compound.

The fluorine compound is a compound capable of dissociating into fluorine ions or polyatomic fluorine ions in the etching liquid composition.The fluorine compound is a component that etches Ga-YO membranes, removes residues generated during etching, and also increases the etching rate. It is an effective secondary oxidant. The type of the fluorine compound is not particularly limited, and specific examples thereof include hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), ammonium bifluoride (NH ₄ HF ₂ ), ammonium fluoride (NH ₄ BF ₄ ), and fluoride Potassium (KF), Potassium Bifluoride (KHF ₂ ), Potassium Borofluoride (KBF ₄ ), Sodium Fluoride (NaF), Sodium Bifluoride (NaHF ₂ ), Aluminum Fluoride (AlF ₃ ), Boron Fluoride Acids (HBF ₄ ), lithium fluoride (LiF), calcium fluoride (CaF ₂ ), and the like, and these may be used alone or in combination of two or more thereof.

The fluorine compound may be included in an amount of 2% by weight or less in 100% by weight of the etching liquid composition, preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight. In this content range, the Ga—Y—O film is etched in an appropriate amount and the etching profile is also excellent. When the content is more than 2% by weight, damage may be made to a substrate such as glass and an insulating film containing silicon.

In addition, the etchant composition may further include an organic acid, a salt thereof, or a mixture thereof.

An organic acid, a salt thereof, or a mixture thereof is a component that maintains a constant etching profile over time of the treatment sheet to control the etching rate of the Cu-X film and the Ga-Y-O film to obtain a desired side etching. Specific examples of organic acids include acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, Salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, propenoic acid, and the like. These may be used alone or in combination of two or more thereof. The salts of the organic acids include potassium salts, sodium salts and ammonium salts of the above organic acids, and these may be used alone or in combination of two or more thereof.

The organic acid, a salt thereof, or a mixture thereof may be included in an amount of 15% by weight or less in 100% by weight of the etching liquid composition, preferably 0.1 to 15% by weight, more preferably 4 to 10% by weight. If the content is more than 15% by weight, the over-etching phenomenon occurs to increase the lateral etching phenomenon and it is difficult to maintain a constant etching profile during the progress of the treatment.

In addition, the etchant composition may further include nitrate, sulfate, perchlorate, or a mixture thereof as an auxiliary oxidant to assist in etching the persulfate and the inorganic acid. They may be included in an amount of 0.1 to 10% by weight in a total of 100% by weight of the etchant composition. In this content range, excellent etching profiles of Cu-X and Ga-Y-O films can be obtained.

In addition, the etchant composition may further include a chelating agent.

Chelating agent is a component that can maintain a constant etching profile during the progress of the treatment sheet to obtain the desired taper angle by controlling the etching rate of the Cu-X film and Ga-Y-O film. Specific examples include nitrilotriacetic acid (NTA), ethylenedimitate acetic acid (EDTA), imino diacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), aminotri (methylenephosphonic acid) (ATMP), 1-hydride Oxyethane (1,1-diylbisproponic acid) (HEDP), ethylenediaminetetra (methyleneproponic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP); Alanine compounds; Aminobutyric acid compounds; Glutamic acid compounds; Glycine compounds; Sarcosine compounds; Citric acid compounds; Water-soluble compounds, such as a polyphosphoric acid compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The chelating agent may be included in 3% by weight or less of the total 100% by weight of the etchant composition, preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight. If the content is more than 3% by weight, it is difficult to maintain a constant profile when the treated sheet progresses over time, and an overetching phenomenon may occur and a taper angle may be lowered.

The kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is good that the specific resistance value is 18 kPa / cm or more as deionized distilled water for a semiconductor process.

Water may be included in the balance in a total of 100% by weight of the etchant composition.

The etchant composition of the present invention may further include one or more additives such as an etching regulator, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH regulator, etc. together with the above components.

The etchant composition of the present invention configured as described above is composed of a copper-based metal film such as a copper single film, a copper alloy film, or a laminated film thereof, and indium oxide (In ₂ O ₃ ), zinc oxide together with gallium oxide (Ga ₂ O ₃ ). Ga-YO films containing (ZnO) or mixtures thereof are particularly useful for uniformly batch wet etching at high etching rates. Through this, it is possible to simplify the etching process and improve the productivity.

In addition, the etchant composition of the present invention can be used not only for the manufacture of flat panel displays such as liquid crystal displays but also for the manufacture of memory semiconductor displays and the like.

The TFT may be manufactured by a method including a step of forming a pattern by collectively etching a Cu-X film and a Ga-Y-O film using the etching solution composition of the present invention.

The manufacturing method of TFT is not specifically limited. For example, forming a Cu-X film and a Ga-Y-O film which are wiring materials for source / drain electrodes on a substrate; Forming a photoresist in an optional region on the formed Ga—Y—O film; Forming a pattern by wet etching the Cu-X film and the Ga-Y-O film with the etching solution composition of the present invention using the formed photoresist as a mask.

In addition, when the Ga-Y-O film and the Cu-X film, which are the wiring materials for the source / drain electrodes, are formed on the substrate in this order, the photoresist can be formed in an optional region on the formed Cu-X film.

According to such a method, metal wiring, that is, source / drain wiring, can be easily formed, and the TFT can be enlarged.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example

Example 1

10% by weight of ammonium persulfate (APS), 5% by weight of nitric acid (HNO ₃ ) and 5% by weight of sulfuric acid (H ₂ SO ₄ ), ₂ % by weight of 5-aminotetrazole (ATZ) and 100% by weight The remaining amount of water The etchant composition was prepared to be 180 kg.

Example 2-12, Comparative Example 1-7

The same procedure as in Example 1, except that the ingredients and contents as shown in Table 1 were used. At this time, the content is% by weight.

division APS Inorganic acids ATZ ABF Organic acid / salt salt Chelating agents Kinds content Kinds content Kinds content Kinds content Example
One 10 HNO ₃
H ₂ SO ₄ 5
5 2 - - - - - - - Example
2 10 HNO ₃
H ₂ SO ₄ 5
5 2 - AA
AcOH 3
7 - - - - Example
3 10 HNO ₃
H ₂ SO ₄ 5
5 2 - - - KNO ₃ One - - Example
4 10 HNO ₃
H ₂ SO ₄ 5
5 2 - - - - - IDA
EDTA One
0.5 Example
5 10 HNO ₃
H ₂ SO ₄ 5
5 2 - AA
AcOH 3
7 KNO ₃ One - - Example
6 10 HNO ₃
H ₂ SO ₄ 5
5 2 - AA
AcOH 3
7 KNO ₃ One IDA
EDTA One
0.5 Example
7 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 - - - - - - Example
8 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 AA
AcOH 3
7 - - - - Example
9 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 - - KNO ₃ One - - Example
10 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 - - - - IDA
EDTA One
0.5 Example
11 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 AA
AcOH 3
7 KNO ₃ One - - Example
12 10 HNO ₃
H ₂ SO ₄ 5
5 2 0.5 AA
AcOH 3
7 KNO ₃ One IDA
EDTA One
0.5 Comparative Example
One 10 HNO ₃
H ₂ SO ₄ -
0.5 2 - - - - - - - Comparative Example
2 10 HNO ₃
H ₂ SO ₄ 5
5 6 - - - - - - - Comparative Example
3 10 HNO ₃
H ₂ SO ₄ 5
5 0.1 - - - - - - - Comparative Example
4 10 HNO ₃
H ₂ SO ₄ 5
5 - 0.5 - - - - - - Comparative Example
5 10 HNO ₃
H ₂ SO ₄ 5
5 6 0.5 - - - - - - Comparative Example
6 10 HNO ₃
H ₂ SO ₄ -
0.5 2 0.5 AA
AcOH 3
7 - - - - Comparative Example
7 10 HNO ₃
H ₂ SO ₄ 5
5 0.1 0.5 AA
AcOH 3
7 KNO ₃ One IDA
EDTA One
0.5 APS: ammonium persulfate
ATZ: 5-aminotetrazole
ABF: ammonium bifluoride
AA: ammonium acetate
AcOH: acetic acid
KNO ₃ : Potassium Nitrate
IDA: iminodiacetic acid
EDTA: ethylenediaminetetraacetic acid

Test Example

<Etch Characteristic Evaluation>

A gallium-containing metal oxide film (Ga-Zn-O film or Ga-In-Zn-O film) was sputtered on the glass, and a copper-based metal film made of pure copper was sputtered on this gallium-containing metal oxide film. After this copper-based metal film A specimen was patterned by cutting a substrate having a photoresist patterned into a shape on the substrate to a size of 550 mm × 650 mm using a diamond knife.

The etchant composition prepared in a spray-type etching system (ETCHER (TFT), manufactured by SEMES) was placed, and the temperature was set at 30 캜 and then heated. Thereafter, the etching process was performed after the temperature reached 30 占 0.1 占 폚. The total etching time was 60% based on the Ending Point Detector (EPD) time. When the etching was completed, the specimen was injected. After the etching was completed, the substrate was washed with deionized water, dried using a hot air drier, and photoresist was removed using a photoresist stripper. After the cleaning and drying, the electron scanning microscope (SEM) (S-4700, HITACHI Co., Ltd.) was used to evaluate the etching characteristics such as the change of the critical dimension (CD) skew, the taper angle, and the damage of the metal oxide film.

<Evaluation Criteria>

◎: very good (CD Skew ≤ 1 μm, taper angle: 40-60 °)

Good: Excellent (1 탆 <CD Skew ≤ 1.5 탆, taper angle: 30-60 °)

?: Good (1.5 탆 <CD Skew ≤ 2 탆, taper angle: 30-60 °)

X: defective (oxide film loss or residue)

division Etch characteristics Membrane type Evaluation results Example 1 Ga-Zn-O / Cu ◎ Example 2 Ga-Zn-O / Cu ◎ Example 3 Ga-Zn-O / Cu ◎ Example 4 Ga-Zn-O / Cu ◎ Example 5 Ga-Zn-O / Cu ◎ Example 6 Ga-Zn-O / Cu ◎ Example 7 Ga-In-Zn-O / Cu ◎ Example 8 Ga-In-Zn-O / Cu ◎ Example 9 Ga-In-Zn-O / Cu ◎ Example 10 Ga-In-Zn-O / Cu ◎ Example 11 Ga-In-Zn-O / Cu ◎ Example 12 Ga-In-Zn-O / Cu ◎ Comparative Example 1 Ga-Zn-O / Cu × Comparative Example 2 Ga-Zn-O / Cu △ Comparative Example 3 Ga-Zn-O / Cu × Comparative Example 4 Ga-In-Zn-O / Cu × Comparative Example 5 Ga-In-Zn-O / Cu △ Comparative Example 6 Ga-In-Zn-O / Cu × Comparative Example 7 Ga-In-Zn-O / Cu ×

As shown in Table 2, the etching liquid composition of Examples 1 to 12 containing the composition of the present invention in an optimal content at the time of the batch wet etching of the Cu-X film and Ga-YO film compared to the etching solution composition of Comparative Examples 1 to 7 An excellent etching profile can be obtained, and excellent etching characteristics without damage to the glass substrate and no loss and residue of the metal film are shown. In particular, in the case of including an organic acid compound, an inorganic salt, a chelating agent or a mixture thereof together with a persulfate, an inorganic acid and a cyclic amine compound, the effect is more preferable.

Claims (14)

An etching solution composition of a copper-based metal film / gallium-containing metal oxide film comprising 5 to 20% by weight of persulfate, 1 to 15% by weight of an inorganic acid, 0.3 to 5% by weight of a cyclic amine compound, and a residual amount of water.
The etching solution composition according to claim 1, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
The etchant composition according to claim 1, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid.
The compound according to claim 1, wherein the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine compound And at least one selected from the group consisting of pyrimidine compounds, pyrrole compounds, pyrrolidine compounds and pyrroline compounds, an etching liquid composition of a copper-based metal film / gallium-containing metal oxide film.
The etching liquid composition of Claim 1 which further contains 0.01 to 2 weight% of fluorine compounds .
The fluorine compound of claim 5, wherein the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium borofluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, lithium fluoride and fluoride. At least one selected from the group consisting of calcium, etching liquid composition of the copper-based metal film / gallium-containing metal oxide film.
The etching liquid composition according to claim 1, further comprising 0.1 to 15% by weight of an organic acid, a salt thereof, or a mixture thereof.
The organic acid according to claim 7, wherein the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, sulfostone An etching liquid composition of a copper-based metal film / gallium-containing metal oxide film, which is at least one member selected from the group consisting of nitric acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and propene acid.
The etching liquid composition of Claim 7 whose salt is a potassium salt, a sodium salt, or an ammonium salt.
The etchant composition of claim 1, further comprising 0.1 to 10% by weight of at least one selected from the group consisting of nitrates, sulfates and perchlorates.
The etching liquid composition of Claim 1 which further contains 0.01 to 3 weight% of a chelating agent.
The method of claim 1, wherein the copper-based metal film is a copper single layer containing at least one member from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or etching liquid composition of a copper-type metal film / gallium containing metal oxide film which is these laminated films.
The etchant composition according to claim 1, wherein the gallium-containing metal oxide film is a film containing gallium oxide, indium oxide, zinc oxide or a mixture thereof.
A method of manufacturing a thin film transistor comprising a step of forming a pattern by collectively etching a copper-based metal film and a gallium-containing metal oxide film with the etching liquid composition of any one of claims 1 to 13.