KR101766775B1 - An etching solution composition for metal layer containing copper/metal oxide layer containing gallium - Google Patents

Abstract

More particularly, the present invention relates to an etchant composition for a copper-based metal film / gallium-containing metal oxide film, which comprises 5 to 20% by weight of persulfate, 1 to 15% by weight of inorganic acid, 0.1 to 5% To 5% by weight, and the balance of water, the copper-based metal film and the metal oxide film containing indium oxide, zinc oxide or a mixture thereof together with gallium or gallium oxide can be uniformly wet-etched uniformly at a high etching rate To an etching solution composition of a copper-based metal film / gallium-containing metal oxide film which can simplify an etching process and improve productivity.

Description

TECHNICAL FIELD [0001] The present invention relates to an etching solution composition for a copper-based metal film / gallium-containing metal oxide film,

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

A typical example of an electronic circuit for driving a semiconductor device and a flat panel display device is a thin film transistor (TFT). The manufacturing process of a TFT is generally composed of forming a metal film as a gate and a data wiring material on a substrate, forming a photoresist in a selective region of the metal film, and etching the upper metal film using the photoresist as a mask.

Typically, as the gate and data wiring material, a copper single film or copper alloy film containing copper having good electrical conductivity and low resistance and a metal oxide film having excellent interfacial adhesion to these films are used. In recent years, a film containing indium oxide, zinc oxide, or a mixture thereof together with gallium oxide has been used as a metal oxide film in order to improve the performance of a TFT. However, this metal oxide film has a high charge mobility and can increase the operation speed of the TFT, but has a disadvantage in that it is difficult to process, particularly to etch.

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

The present invention relates to a copper-based metal film and an etching solution of a copper-based metal film / gallium-containing metal oxide film capable of quickly and uniformly wet-etching a metal oxide film containing indium oxide, zinc oxide or a mixture thereof together with gallium or gallium oxide And to provide a composition.

1. A copper-based metal film / gallium-containing metal oxide comprising 5 to 20 wt% of persulfate, 1 to 15 wt% of inorganic acid, 0.1 to 5 wt% of phosphate, 0.3 to 5 wt% of cyclic amine compound, Lt; / RTI >

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

3. The etchant composition of copper-based metal / gallium-containing metal oxide film according to item 1, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.

4. In paragraph 1 above, the phosphate is selected from the group consisting of ammonium phosphate, potassium phosphate, sodium phosphate, ammonium monohydrogenphosphate, ammonium dihydrogenphosphate, potassium monohydrogenphosphate, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium dihydrogenphosphate, (1-hydroxy-1-phosphonoethyl) phosphonic acid, ammonium (1-hydroxy-1-phosphonoethyl) -1-phosphonoethyl) sodium phosphonate, wherein the copper-based metal film / gallium-containing metal oxide film is at least one selected from the group consisting of aluminum oxide,

5. The method of claim 1, wherein the cyclic amine compound is selected from the group consisting of 5-aminotetrazole, tolythriazole, benzotriazole, methylbenzotriazole, imidazole compounds, indole compounds, pyridine compounds, pyrazole compounds, Wherein at least one selected from the group consisting of a metal compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, and a pyrrole compound is used.

6. The etchant composition for a copper-based metal film / gallium-containing metal oxide film according to item 1, further comprising 0.01 to 2% by weight of a fluorine compound .

7. The fluorine compound as described in 6 above, wherein the fluorine compound is at least one selected from the group consisting of fluoric acid, ammonium fluoride, ammonium fluoride, ammonium fluoride, potassium fluoride, potassium bisulfide, potassium fluoroborate, sodium fluoride, sodium bisulfide, And calcium fluoride, wherein the copper-based metal film / gallium-containing metal oxide film is at least one selected from the group consisting of calcium fluoride and calcium fluoride.

8. The etching solution composition for a copper-based metal film / gallium-containing metal oxide film according to item 1, further comprising 0.1 to 15% by weight of an organic acid, a salt thereof or a mixture thereof.

9. The composition of claim 8 wherein the organic acid is selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, Wherein at least one selected from the group consisting of sulphosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid and propenoic acid is used.

10. The etchant composition of copper-based metal / gallium-containing metal oxide film according to item 8 above, wherein the salt is a potassium salt, a sodium salt or an ammonium salt.

11. The etchant composition of copper-based metal / gallium-containing metal oxide film according to item 1, further comprising 0.1 to 10% by weight of at least one selected from the group consisting of nitrate, sulfate and perchlorate.

12. The etchant composition of a copper-based metal film / gallium-containing metal oxide film, which further comprises 0.01 to 3% by weight of a chelating agent.

13. The copper-based metal film according to 1 above, wherein the copper-based metal film comprises a copper single film containing at least one selected from the group consisting of copper, a nitride thereof and an oxide thereof; At least one member selected from the group consisting of copper, a nitride thereof and an oxide thereof and at least one member selected 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 a laminated film of the above-mentioned copper-based metal film / gallium-containing metal oxide film.

14. The etchant composition of the copper-based metal film / gallium-containing metal oxide film according to item 1 above, wherein the gallium-containing metal oxide film is a film containing gallium oxide, indium oxide, zinc oxide or a mixture thereof.

15. A method for fabricating a thin film transistor, comprising: forming a pattern by collectively etching a copper-based metal film and a gallium-containing metal oxide film with an etchant composition according to any one of items 1 to 14 above.

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

Further, the etchant composition of the present invention can prevent an undercut from being formed in the gallium-containing metal oxide film.

In addition, the etchant composition of the present invention does not require expensive equipment, does not damage equipment, and is advantageous in large-scale and economical advantage.

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

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 in which a copper-based metal film / a gallium-containing metal oxide film are stacked in this order, a gallium-containing metal oxide 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, for example, a triple film of a copper-based metal film / gallium-containing metal oxide film / copper- A triple layer of a metal / gallium-containing metal oxide layer, a copper-based metal layer / a gallium-containing metal oxide layer / a copper-based metal layer / a gallium-containing metal oxide layer / a copper-based metal layer. At this time, the thicknesses of the copper-based metal film and the gallium-containing metal oxide film are not particularly limited.

In the present invention, the "copper-based metal film" may be a copper-containing film composed of at least one selected from the group consisting of pure copper, nitride thereof and oxides thereof, as a constituent component of the film. Also, it is possible to use at least one selected from the group consisting of pure copper, a nitride thereof and an oxide thereof, and at least one selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag) (M) selected from the group consisting of Mn, Fe, Zr, Nb, Mo, Pd, hafnium, tantalum Ta and tungsten For example, a copper alloy film composed of copper and manganese, or a copper alloy film composed of copper, magnesium, and aluminum. The copper-based metal film may be a laminated film of a copper single film and a copper alloy film. Hereinafter, the copper-based metal film is represented by Cu-X.

In the present invention, gallium-containing metal oxide film, the gallium (Ga) or gallium oxide (Ga ₂ O ₃₎ and with indium oxide (In ₂ O _3), zinc oxide (ZnO) or a metal, including mixtures thereof Oxide film. Normally, Ga-YO (Y can be represented by In, Zn or In-Zn), and is expressed as follows.

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, phosphate, cyclic amine compound and water.

More specifically, it comprises 5 to 20% by weight of persulfate, 1 to 15% by weight of inorganic acid, 0.1 to 5% by weight of phosphate, 0.3 to 5% by weight of cyclic amine compound and the balance water.

The persulfate is the main oxidizing agent for etching Cu-X film and Ga-YO film. Specific examples thereof include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and potassium persulfate (K ₂ S ₂ O ₈ ) Mix more than one species.

The persulfate is preferably contained in an amount of 5 to 20% by weight, more preferably 7 to 12% by weight, based on 100% by weight of the total amount of the etching solution composition. In this content range, the Cu-X film and the Ga-Y-O film are etched at a proper 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 may be slow. If the content is more than 20% by weight, the etching speed may be entirely accelerated and the process may be difficult to control.

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

The inorganic acid may be contained in an amount of 1 to 15% by weight, preferably 2 to 10% by weight, based on 100% by weight of the total amount of the etching liquid composition. In this content range, the Cu-X film and the Ga-Y-O film are etched at a proper amount and the etching profile is also excellent. If the content is less than 1% by weight, the etching rate may be lowered and the etching profile may become poor and residues may occur. If the content is more than 15% by weight, an excessive angle may occur, cracks may occur in the photoresist, The etching solution composition may penetrate and the wiring may be short-circuited.

Phosphate is the main component for etching Cu-X film and Ga-Y-O film. In the present invention, phosphates include not only conventional phosphates but also phosphorous acids and phosphites. Specific examples thereof include conventional phosphates such as ammonium phosphate, potassium phosphate, sodium phosphate, ammonium monohydrogenphosphate, ammonium dihydrogenphosphate, potassium monohydrogenphosphate, potassium dihydrogenphosphate, sodium monohydrogenphosphate and sodium dihydrogenphosphate; (1-hydroxy-1-phosphonoethyl) phosphonic acid; Such as ammonium (1-hydroxy-1-phosphonoethyl) phosphonate, potassium (1-hydroxy-1-phosphonoethyl) phosphonate or sodium (1-hydroxy-1-phosphonoethyl) Phosphate; and the like. As commercially available products, Dequest 2010, Dequest 2000, Dequest 2066a, Dequest 2006, Dequest P9000, or the like may be used. These may be used alone or in combination of two or more.

The phosphate may be contained in an amount of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, and more preferably 1.7 to 2.2% by weight, based on 100% by weight of the etchant composition. The Cu-X film and the Ga-Y-O film are suitably etched in the above content range, and the etching profile is also excellent. When the content is less than 0.1% by weight, the etching rate is generally accelerated, which is disadvantageous for forming a fine pattern. When the content is more than 5% by weight, the etching rate is low and residues may occur.

The cyclic amine compound is a component that forms an etching profile when the Cu-X film and the Ga-Y-O film are etched. Specific examples thereof include 5-aminotetrazole, tolythriazole, benzotriazole, methylbenzotriazole, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds, A pyrrole compound, a pyrrole compound, and the like. These compounds may be used alone or in admixture of two or more.

The cyclic amine compound may be contained in an amount of 0.3 to 5% by weight, preferably 0.5 to 3% by weight, based on 100% by weight of the total amount of the etching solution composition. In the case of this content range, it is possible to form an appropriate etching rate and taper angle of the copper-based metal film and adjust the side etching amount. If the content is less than 0.5% by weight, it is difficult to control the etching speed of the Cu-X film sufficiently, so that an excessive angle may occur. When the content exceeds 5% by weight, the etching speed of the Cu- .

The etchant composition may further comprise a fluorine compound.

The fluorine compound is a compound which can dissociate into fluorine ions or polyatomic fluorine ions in the etching solution composition. It is a component which etches a Ga-YO film and removes residues generated during etching and increases the etching rate. In particular, Is an effective auxiliary oxidant. The kind of the fluorine compound is not particularly limited and specific examples include hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), ammonium bifluoride (NH ₄ HF ₂ ), ammonium borofluoride (NH ₄ BF ₄ ) potassium (KF), medium heat Chemistry potassium (potassium bifluoride, KHF _2), boron potassium fluoride (KBF _4), sodium fluoride (NaF), medium heat sodium (sodium bifluoride, NaHF _2), ammonium fluoride (AlF _3), boron trifluoride (HBF ₄ ), lithium fluoride (LiF), calcium fluoride (CaF ₂ ), etc. These may be used alone or in combination of two or more.

The fluorine compound may be contained in an amount of 2% by weight or less, preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on 100% by weight of the total amount of the etching solution composition. In the case of this content range, the Ga-Y-O film is etched at a proper amount and the etching profile is also excellent. If the content is more than 2% by weight, the substrate such as glass and the insulating film containing silicon may be damaged.

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

The organic acid, its salt, or a mixture thereof is a component that allows a constant etch profile to be maintained over time in order to obtain a desired side etching by controlling the etch rate of the Cu-X film and the Ga-Y-O film. Specific examples of the organic acid include acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, Salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, propenoic acid, etc. These may be used alone or in admixture of two or more. Examples of salts of organic acids include potassium salts, sodium salts and ammonium salts of organic acids, and these salts may be used singly or in combination of two or more.

The organic acid, its salt or a mixture thereof may be contained in an amount of 15% by weight or less, preferably 0.1 to 15% by weight, more preferably 4 to 10% by weight, based on 100% by weight of the total amount of the etching solution composition. When the content is more than 15% by weight, overexposure phenomenon occurs and lateral etching becomes large, and it is difficult to maintain a constant etching profile when the number of treatments is reduced over time.

In addition, the etchant composition may further comprise nitrates, sulfates, perchlorates, or mixtures thereof as auxiliary oxidants to assist in etching the persulfate and inorganic acid. These may be contained in an amount of 0.1 to 10% by weight based on 100% by weight of the total of the etching liquid composition. In this content range, an excellent etching profile of the Cu-X film and the Ga-Y-O film can be obtained.

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

The chelating agent is a component that can maintain a constant etch profile when the etching number of the Cu-X film and the Ga-Y-O film is adjusted to obtain a desired taper angle over time. Specific examples thereof include nitrile compounds such as nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), aminotri (methylenephosphonic acid) Hydroxyethane (1,1-diyl bispropionic acid) (HEDP), ethylenediamine tetra (methylene propionic acid) (EDTMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP); Alanine compounds; Aminobutyric acid compounds; Glutamic acid compounds; Glycine-based compounds; Sarcosine compounds; Citric acid compounds; Water-soluble compounds such as polyphosphoric acid-based compounds, and the like. These may be used alone or in admixture of two or more.

The chelating agent may be contained in an amount of 3% by weight or less, preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight, based on 100% by weight of the total amount of the etching solution composition. When the content is more than 3% by weight, it is difficult to maintain a constant profile when the number of treatments is lengthened, and overeating phenomenon may occur and the taper angle may be lowered.

The kind of water is not particularly limited, and it is preferably deionized distilled water. More preferably, it is deionized distilled water for semiconductor processing and has a resistivity value of 18 MΩ / cm or more.

Water may be contained in the balance in 100 wt% of the total amount of the etching solution composition.

The etchant composition of the present invention may further contain at least one additive such as an etch control agent, a surfactant, a sequestering agent, a corrosion inhibitor, and a pH adjuster together with the above components.

Etching liquid composition of the present invention constructed in this manner is copper alone film, copper alloy film or a copper-based metal film, a gallium oxide, such as a laminated film (Ga ₂ O ₃₎ and indium oxide with (In ₂ O _3), zinc oxide (ZnO), or mixtures thereof, is particularly useful for uniform wet bulk etch at high etch rates. This makes it possible to simplify the etching process and improve the productivity.

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

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

The manufacturing method of the TFT is not particularly limited. For example, a step of forming a Cu-X film and a Ga-Y-O film as source / drain electrode wiring materials on a substrate; Forming a photoresist in a selective region on the Ga-Y-O film formed; And patterning the Cu-X film and the Ga-Y-O film using the formed photoresist as a mask in a batch wet etching process using the etchant composition of the present invention.

When a Ga-Y-O film and a Cu-X film which are wiring material for source / drain electrodes are formed in this order on a substrate on a substrate, a photoresist can be formed in a selective region on the formed Cu-X film.

According to this method, metal wirings, that is, source / drain wirings can be easily formed, and the size of the TFT can be increased.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  One

Ammonium persulfate (ammonium persulfate, APS) 10% by weight, nitric acid (HNO ₃₎ 5% by weight of sulfuric acid (H ₂ SO ₄₎ 5% by weight, 5% by weight of a phosphate, 5-amino-tetrazole (aminotetrazole, ATZ) 5 wt. % And a total amount of 100% by weight The etchant composition was prepared to be 180 kg.

Example  2-12, Comparative Example  1-7

The components and contents as shown in Table 1 below were used in the same manner as in Example 1. Here, the content is% by weight.

division APS Inorganic acid ATZ phosphate ABF Organic acid / salt salt Chelating agent Kinds content Kinds content Kinds content Kinds content Example
One 10 HNO ₃
H ₂ SO ₄ 5
5 5 5 - - - - - - - Example
2 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 - AA
AcOH 3
7 - - - - Example
3 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 - - - KNO ₃ One - - Example
4 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 - - - - - IDA
EDTA One
0.5 Example
5 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 - AA
AcOH 3
7 KNO ₃ One - - Example
6 10 HNO ₃
H ₂ SO ₄ 5
5 2 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 2 0.5 - - - - - - Example
8 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 0.5 AA
AcOH 3
7 - - - - Example
9 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 0.5 - - KNO ₃ One - - Example
10 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 0.5 - - - - IDA
EDTA One
0.5 Example
11 10 HNO ₃
H ₂ SO ₄ 5
5 2 2 0.5 AA
AcOH 3
7 KNO ₃ One - - Example
12 10 HNO ₃
H ₂ SO ₄ 5
5 2 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 5 8 - - - - - - - Comparative Example
5 10 HNO ₃
H ₂ SO ₄ 5
5 - 0.5 - - - - - - Comparative Example
6 10 HNO ₃
H ₂ SO ₄ 5
5 6 0.5 - - - - - - Comparative Example
7 10 HNO ₃
H ₂ SO ₄ -
0.5 2 0.5 AA
AcOH 3
7 - - - - Comparative Example
8 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 < RTI ID = 0.0 >
ATZ: 5-aminotetrazole
Phosphate: Dequest 2010 ((1-hydroxy-1-phosphonoethyl) phosphonic acid)
(1-hydroxy-1-phosphonoethyl) phosphonic acid
ABF: Ammonium bifluoride
AA: Ammonium acetate
AcOH: acetic acid
KNO ₃ : Potassium nitrate
IDA: iminodiacetic acid
EDTA: Ethylenediaminetetraacetic acid (EDTA)

Test Example

< Etching  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 the gallium-containing metal oxide film. Thereafter, a substrate having a pattern of photoresist patterned in a certain shape on the copper-based metal film was cut into a size of 550 mm × 650 mm using a diamond knife to prepare a specimen.

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 etch time was 60% based on EPD (Ending Point Detector) 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. Etching characteristics such as changes in critical dimension (CD) skew, taper angle, metal oxide film damage, etc. were evaluated using a scanning electron microscope (SEM) (S-4700, HITACHI) after cleaning and drying.

<Evaluation Criteria>

⊚: very excellent (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 disappearance or residue)

division Etch characteristics Film 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-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 × Comparative Example 8 Ga-In-Zn-O / Cu ×

As shown in Table 2, the etchant compositions of Examples 1 to 12, in which the composition of the present invention was optimally contained, had a Cu-X film and a Ga-YO film as a whole when wet- An excellent etching profile can be obtained, no damage to the glass substrate, and disappearance of the metal film and excellent etching characteristics without residue. Particularly, when the organic acid compound, the inorganic salt, the chelating agent or the mixture thereof is contained together with the persulfate, the inorganic acid and the cyclic amine compound, the effect is more preferable.

Claims (15)

A copper-based metal film and a gallium-containing metal film, wherein the copper-based metal film and the gallium-containing metal film comprise 5-20 wt% persulfate, 2-10 wt% inorganic acid, 1.7-2.2 wt% phosphorous acid or phosphite, 0.3-5 wt% Etchant composition of an oxide film.
The etchant composition of 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 of 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.
[2] The phospholipid according to claim 1, wherein the phosphorous acid or phosphite is at least one selected from the group consisting of (1-hydroxy-1-phosphonoethyl) phosphonic acid, (1-hydroxy- (1-hydroxy-1-phosphonoethyl) phosphonate and sodium (1-hydroxy-1-phosphonoethyl) phosphonate, and a gallium-containing metal oxide film.
The cyclic amine compound according to claim 1, wherein the cyclic amine compound is at least one compound selected from the group consisting of 5-aminotetrazole, tolythriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, , A pyrimidine-based compound, a pyrrole-based compound, a pyrrolidine-based compound, and a pyrroline-based compound, and a gallium-containing metal oxide film.
The etchant composition of a copper-based metal film and a gallium-containing metal oxide film according to claim 1, further comprising 0.01 to 2% by weight of a fluorine compound .
7. The method of claim 6, wherein the fluorine compound is selected from the group consisting of fluoric acid, ammonium fluoride, ammonium fluoride, ammonium fluoride, potassium fluoride, potassium bisulfide, potassium fluoroborate, sodium fluoride, sodium bisulfide, aluminum fluoride, boron fluoride, Calcium, and a gallium-containing metal oxide film.
The etchant composition of a copper-based metal film and a gallium-containing metal oxide film according to claim 1, further comprising 0.1 to 15% by weight of an organic acid, a salt thereof or a mixture thereof.
The method of claim 8 wherein the organic acid is selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, Wherein at least one element selected from the group consisting of sulfuric acid, salicylic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid and propenoic acid.
9. The etchant composition of claim 8, wherein the salt is a potassium salt, a sodium salt or an ammonium salt, the copper-based metal film and the gallium-containing metal oxide film.
The etchant composition according to claim 1, further comprising 0.1 to 10% by weight of at least one selected from the group consisting of nitrate, sulfate and perchlorate.
The etchant composition of a copper-based metal film and gallium-containing metal oxide film according to claim 1, further comprising 0.01 to 3% by weight of a chelating agent.
The copper-based metal film according to claim 1, wherein the copper-based metal film is a copper-only film containing at least one selected from the group consisting of copper, a nitride thereof and an oxide thereof; At least one member selected from the group consisting of copper, a nitride thereof and an oxide thereof and at least one member selected 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 a laminated film of the above-mentioned copper-based metal film and gallium-containing metal oxide film.
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, and a copper-based metal film and a gallium-containing metal oxide film.
A method for manufacturing a thin film transistor, comprising the 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 14.