KR101804573B1

KR101804573B1 - An etching solution composition

Info

Publication number: KR101804573B1
Application number: KR1020100098368A
Authority: KR
Inventors: 이석준; 신혜라; 권오병; 이유진
Original assignee: 동우 화인켐 주식회사; 삼성디스플레이 주식회사
Priority date: 2009-10-29
Filing date: 2010-10-08
Publication date: 2017-12-06
Also published as: KR20110047130A; CN102753652B; JP5706434B2; WO2011052909A3; CN102753652A; JP2013509702A; WO2011052909A2

Abstract

The present invention relates to a composition comprising 1 to 15% by weight of hydrogen peroxide; 0.1 to 10% by weight of inorganic acid; 0.01 to 5% by weight of a fluorine compound; And an aluminum-lanthanum alloy film and a titanium-based metal film, which comprises a remaining amount of water, an aluminum-lanthanum alloy film and a titanium-based metal film.

Description

AN ETCHING SOLUTION COMPOSITION [0001]

The present invention relates to an etchant composition of a triple-layer film made of an indium-based metal film, an aluminum-lanthanum alloy film and a titanium-based metal film.

The process of forming a metal wiring on a substrate in a flat panel display typically includes a process of forming a metal film by sputtering, a process of applying a photoresist on a metal film, exposing and developing it to form a photoresist in a selective region, And etching the film. It also includes cleaning processes before and after individual unit processes. This etch process refers to a process that uses a photoresist as a mask to leave a metal film in a selective region. As the etching process, dry etching using plasma or wet etching using an etching solution is usually used.

On the other hand, a transparent conductive film which is an indium based metal film is mainly used as a pixel electrode in a flat panel display. As the source / drain electrode, an aluminum lanthanum alloy film such as Al-La-X (X = Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, , Sn, Fe, Si, Mo, Pt, and C). A metal film containing titanium as an adhesive film is mainly used for bonding the source / drain electrode and the insulating film to the lower portion of the source / drain electrode.

Conventionally, in order to etch the pixel electrode, the source / drain electrode, and the adhesive film of the flat panel display device, it has been necessary to use different etchant compositions for each electrode. This complicates the etching process and is uneconomical.

It is an object of the present invention to provide an etchant composition capable of efficient batch etching of a triple-layer film made of an indium-based metal film, an aluminum-lanthanum alloy film and a titanium-based metal film.

In order to achieve the above object, the present invention relates to a composition comprising 1 wt% to 15 wt% of hydrogen peroxide, 0.1% to 10% by weight of inorganic acid; From 0.01% to 5% by weight of a fluorine compound; And an aluminum-lanthanum alloy film and a titanium-based metal film.

Preferably, the present invention provides a hydrogen peroxide composition comprising 2 wt% to 12 wt% hydrogen peroxide; 1% to 7% by weight of inorganic acid; 0.1% to 2% by weight of a fluorine compound; And an aluminum-lanthanum alloy film and a titanium-based metal film.

The etchant composition of the present invention is excellent in etching properties for each of the indium-based metal film, the aluminum-lanthanum alloy film and the titanium-based metal film. In addition, since the etchant composition of the present invention has excellent etching properties of an aluminum-lanthanum alloy film and does not cause curling of the upper portion of the Al-La based alloy film, the aluminum-lanthanum alloy film and the titanium- Can be effectively etched in a batch. Further, when the etching solution composition of the present invention is used, the etching process can be significantly simplified and the production amount can be greatly increased.

Hereinafter, the present invention will be described in detail.

The etchant composition of the present invention comprises hydrogen peroxide, inorganic acid, fluorine compound and water.

In the present invention, hydrogen peroxide plays a role of main oxidation. The hydrogen peroxide is preferably contained in an amount of 1% by weight to 15% by weight, and more preferably 2% by weight to 12% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, the surfaces of the indium-based metal film, the aluminum-lanthanum alloy film and the titanium-based metal film can be easily oxidized.

In the present invention, the inorganic acid serves as a supplementary oxidizing agent. The inorganic acid is preferably contained in an amount of 0.1 to 10% by weight, more preferably 1 to 7% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, the surface of the indium-based metal film, the aluminum-lanthanum alloy film, and the titanium-based metal film can be oxidized more easily with the hydrogen peroxide. It is also easy to adjust the etching rate, side etch and taper angle.

The inorganic acid is preferably one selected from the group consisting of nitric acid, sulfuric acid, and a mixture thereof, though not limited thereto.

In the present invention, the fluorine compound serves to etch the surfaces of the indium-based metal film, the aluminum-lanthanum alloy film, and the titanium-based metal film.

The content of the fluorinated compound is preferably 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% with respect to the total weight of the composition. When included in the above range, the surfaces of the oxidized indium based metal film, the aluminum-lanthanum alloy film and the titanium based metal film can be easily and adequately etched.

At this time, the fluorinated compound is preferably a compound capable of dissociating into a fluorine ion or a polyatomic fluorine ion in a dissolved state. For example, the fluorinated compound may be one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride.

The water contained in the etchant composition of the present invention means deionized water. Semiconductor process is used, preferably water of 18 M / cm or more is used. The water is contained in such an amount that the total weight of the etchant composition of the present invention is 100% by weight based on the total weight of the composition.

The etchant composition of the present invention may further include one or more selected from the group consisting of known additives such as an etch control agent, a surfactant, and a pH adjuster in addition to the above-mentioned components.

Meanwhile, in the present invention, the indium-based metal film means a transparent conductive film, which is an indium zinc oxide film (IZO) or an indium tin oxide film (ITO). Further, the aluminum-lanthanum alloy film is an aluminum-lanthanum alloy film containing aluminum as a main component. More specifically, the aluminum-lanthanum alloy film means Al-La or Al-La-X containing at least 90 atomic% of aluminum, at most 10 atomic% of La, and other metal (X) balance. The other metal (X) is composed of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Or a combination of two or more species selected from the group consisting of In addition, the titanium-based metal film is a titanium film or a titanium alloy film containing titanium as a main component.

Hereinafter, the present invention will be described in more detail by way of Examples and Test Examples. However, the scope of the present invention is not limited by the following examples and test examples.

Examples 1 to 7 and Comparative Examples 1 to 6 Preparation of Etchant Composition

The composition of the etchant was prepared to be 180 kg according to the ingredients and composition ratio shown in Table 1 below.

Hydrogen peroxide (% by weight) Nitric acid (wt.%) NH4FHF (wt%) Water (% by weight) Example 1 10 One 0.3 Balance Example 2 10 2 0.2 Balance Example 3 10 2 0.1 Balance Example 4 7 3 0.3 Balance Example 5 7 2 0.2 Balance Example 6 12 One 0.2 Balance Example 7 12 2 0.1 Balance Comparative Example 1 20 One 0.3 Balance Comparative Example 2 10 12 0.3 Balance Comparative Example 3 10 One 0 Balance Comparative Example 4 10 2 6.0 Balance Comparative Example 5 0 2 0.1 Balance Comparative Example 6 10 0 0.1 Balance

Test Example: Characteristic Evaluation of Etchant Composition

As a test substrate, a tri-layer of a-ITO / Al-La-Ni / Ti was deposited on a SiNx layer and a photoresist patterned in a certain shape was used.

The etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were placed in an experimental apparatus (SEMES, model name: ETCHER (TFT)) of a spray-type etching system, and the temperature was set at 30 ° C. Thereafter, after the temperature reached 30 +/- 0.1 DEG C, the etching process was performed. The total etch time was 30% based on EPD. When the etching was completed, the test piece was injected. After the etching was completed, the substrate was washed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist (PR) stripper. After cleaning and drying, the inclination angle of the etching profile, critical dimension (CD) loss, etch residue and underlying film damage were evaluated using a scanning electron microscope (SEM: model name: S-4700, manufactured by Hitachi). The results are shown in Table 2 below.

Board Etching profile Underlying membrane damage Residue Example 1

a-ITO / Al-La-Ni / Ti ◎ none none Example 2 ◎ none none Example 3 ◎ none none Example 4 ○ none none Example 5 ○ none none Example 6 ○ none none Example 7 ○ none none Comparative Example 1 × none none Comparative Example 2 × has exist none Comparative Example 3 × Unetch Comparative Example 4 × has exist none Comparative Example 5 × none has exist Comparative Example 6 × none has exist

[Evaluation Criteria of Etching Profile]

⊚: very good (CD Skew: ≤1 μm, Taper Angle: 40 ° to 80 °)

?: Excellent (CD Skew:? 1.5 m, Taper Angle: 40 to 80)

?: Good (CD Skew:? 2 mu m, Taper Angle: 40 to 80)

X: Bad (metal film disappearance and residue formation)

Referring to Table 2, the etchant compositions of Examples 1 to 7 exhibited excellent etching properties for the a-ITO / Al-La-Ni / Ti triple layer, .

However, in the case of the etching solution composition of Comparative Example 1 in which hydrogen peroxide was excessively contained, the etching profile was extremely poor due to the overexcitation angle of the Al-La-Ni thin film. Further, in the case of the etching solution composition of Comparative Example 2 in which nitric acid was contained in an excess amount, the etching profile defects and the damage of the lower film due to the overexposure angle were observed. In the case of the etching solution composition of Comparative Example 3 in which no fluorine compound was contained, an etch of the upper a-ITO occurred. In the case of the etching solution composition of Comparative Example 4, the damage of the lower film was remarkably increased by the excessive fluorinated compound. In the case of the etching solution compositions of Comparative Example 5 and Comparative Example 6 which did not contain hydrogen peroxide or nitric acid, the etching rate was very slow and the residue and the poor etching profile were observed.

Claims

With respect to the total weight of the composition,
1% to 15% by weight of hydrogen peroxide;
0.1% to 10% by weight of inorganic acid;
From 0.01% to 5% by weight of a fluorine compound; And
Water balance,
Wherein the fluorinated compound is at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride, an aluminum-lanthanum series An alloy film and a titanium-based metal film.

The composition of claim 1, wherein, relative to the total weight of the composition,
2% to 12% by weight of hydrogen peroxide;
1% to 7% by weight of inorganic acid;
0.1% to 2% by weight of a fluorine compound; And
And an aluminum-lanthanum alloy film and a titanium-based metal film.

The method according to claim 1,
Wherein the inorganic acid is one selected from the group consisting of nitric acid, sulfuric acid, and a mixture thereof, and an aluminum-lanthanum alloy film and a titanium-based metal film.

delete

The method according to claim 1,
The aluminum-lanthanum alloy film is an aluminum-lanthanum alloy film represented by Al-La or Al-La-X containing at least 90 atomic% of aluminum, at most 10 atomic% of La, The other metal X is selected from the group consisting of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Or a mixture of two or more species selected from the group consisting of an indium-based metal film, an aluminum-lanthanum alloy film, and a titanium-based metal film.