WO2011052909A2

WO2011052909A2 - Etchant composition

Info

Publication number: WO2011052909A2
Application number: PCT/KR2010/006953
Authority: WO
Inventors: 이석준; 신혜라; 권오병; 이유진
Original assignee: 동우 화인켐 주식회사
Priority date: 2009-10-29
Filing date: 2010-10-12
Publication date: 2011-05-05
Also published as: KR20110047130A; WO2011052909A3; CN102753652A; JP2013509702A; CN102753652B; KR101804573B1; JP5706434B2

Abstract

The present invention relates to an etchant composition for etching a triple film consisting of an indium-based metal film, an aluminum-lanthanum-based alloy film, and a titanium-based metal film, wherein the etchant composition comprises: 1 to 15 wt % of hydrogen peroxide; 0.1 to 10 wt % of inorganic acid; and 0.01 to 5 wt % of a fluorine compound, with the remainder being water.

Description

Etch solution composition

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

In the flat panel display, a process of forming a metal wiring on a substrate is typically a process of forming a metal film by sputtering, a process of forming a photoresist in a selective region by applying a photoresist on a metal film, exposing and developing the metal film, and a metal. It consists of a process of etching the film. Moreover, the washing | cleaning process, etc. before and after an individual unit process are included. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. As an etching process, dry etching using a plasma or the like, or wet etching using an etching solution is generally used.

In the flat panel display device, a transparent conductive film, which is an indium metal film, is mainly used as a pixel electrode. As the source / drain electrodes, an aluminum lanthanum alloy film, that is, Al-La-X (X = Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd , Aluminum alloy film in the form of Sn, Fe, Si, Mo, Pt, C) is mainly used. In addition, a metal film including titanium is mainly used under the source / drain electrodes to bond the source / drain electrodes to the insulating film.

Conventionally, in order to etch the pixel electrode, the source / drain electrode, and the adhesive film of the flat panel display device, a different etchant composition must be used for each electrode. This made the etching process complicated and uneconomical.

SUMMARY OF THE INVENTION An object of the present invention is to provide an etchant composition capable of efficiently collectively etching a triple film made of an indium metal film, an aluminum-lanthanum alloy film, and a titanium metal film.

In order to achieve the above object, the present invention is 1 to 15% by weight of hydrogen peroxide, based on the total weight of the composition; 0.1 wt% to 10 wt% of an inorganic acid; 0.01 wt% to 5 wt% of a fluorine-containing compound; And an indium metal film, an aluminum-lanthanum alloy film, and a titanium metal film including an amount of water remaining therein.

Preferably, the present invention comprises 2 to 12% by weight of hydrogen peroxide; 1 to 7 weight percent of inorganic acid; 0.1 wt% to 2 wt% of a fluorine-containing compound; And an indium metal film, an aluminum-lanthanum alloy film, and a titanium metal film including an amount of water remaining therein.

The etchant composition of the present invention is excellent in etching characteristics for each of the indium-based metal film, aluminum-lanthanum-based alloy film and titanium-based metal film. In addition, the etching liquid composition of the present invention is excellent in etching characteristics of the aluminum-lanthanum-based alloy film, so that curling does not occur on the Al-La-based alloy film. It is possible to efficiently etch a triple layer consisting of. In addition, the use of the etchant composition of the present invention can greatly increase the yield since the etching process is significantly simplified.

Hereinafter, the present invention will be described in detail.

The etchant composition of the present invention includes hydrogen peroxide, an inorganic acid, a fluorine-containing compound, and water.

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

In addition, the inorganic acid in the present invention serves as a secondary oxidant. The inorganic acid is preferably included 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 range is satisfied, the surfaces of the indium metal film, the aluminum-lanthanum alloy film, and the titanium metal film together with the hydrogen peroxide can be more easily oxidized. It also makes it easier to adjust the etch rate, side etch and taper angle.

The inorganic acid is preferably, but not limited to, one selected from nitric acid, sulfuric acid and mixtures thereof.

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

The fluorine-containing compound is preferably included in an amount of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt%, based on the total weight of the composition. When included in the above-described range, it is possible to easily and appropriately etch the surface of the oxidized indium-based metal film, aluminum-lanthanum-based alloy film and titanium-based metal film.

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

Water included in the etchant composition of the present invention means deionized water. A semiconductor process is used, Preferably water of 18 kPa / cm or more is used. The water is included in the balance so that the total weight of the etchant composition of the present invention to 100% by weight relative to the total weight of the composition.

The etchant composition of the present invention may further include one or two or more selected from the group consisting of known additives, for example, an etching control agent, a surfactant, and a pH adjusting agent, in addition to the above-mentioned components.

Meanwhile, in the present invention, the indium metal film means a transparent conductive film, which is an indium zinc oxide film (IZO) or an indium tin oxide film (ITO). In addition, the aluminum-lanthanum-based alloy film means that the aluminum-lanthanum alloy film containing aluminum as a main component. More specifically, the aluminum-lanthanum-based alloy film refers to Al-La or Al-La-X including 90 atomic% or more of aluminum, 10 atomic% or less of La, and the remaining amount of other metals (X). Wherein the other metal (X) is made of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt and C It is preferable that it is 1 type, or 2 or more types selected from the group. In addition, the titanium-based metal film means a titanium film or a titanium alloy film containing titanium as a main component.

Hereinafter, the present invention will be described in more detail with reference to 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, Comparative Examples 1 to 6: Preparation of the etchant composition

To the etchant composition according to the component and composition ratio shown in Table 1 to 180kg was prepared.

Table 1

Test Example: Evaluation of Properties of Etch Liquid Composition

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

The etching liquid composition of Examples 1 to 7, Comparative Examples 1 to 6 was placed in an experimental equipment of a spray etching method (manufactured by SEMES, model name: ETCHER (TFT)), and warmed by setting the temperature to 30 ° C. Then, after the temperature reached 30 ± 0.1 ℃, the etching process was performed. Total etch time was given at 30% based on EPD. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper. After washing and drying, an electron scanning microscope (SEM: manufactured by HITACHI, model name: S-4700) was used to evaluate the inclination angle of the etching profile, the loss of critical dimension (CD), the etching residue and the underlying film damage. The results are shown in Table 2 below.

TABLE 2

[Evaluation Criteria of Etch Profile]

◎: Very good (CD Skew: ≤1㎛, Taper Angle: 40 ° ~ 80 °)

○: Excellent (CD Skew: ≤1.5㎛, Taper Angle: 40 ° ~ 80 °)

△: Good (CD Skew: ≤2㎛, Taper Angle: 40 ° to 80 °)

X: Poor (metal film loss and residue)

Referring to Table 2, the etchant composition of Examples 1 to 7 has an excellent etching profile, no damage to the lower layer and no residue, resulting in excellent etching characteristics for the a-ITO / Al-La-Ni / Ti triple layer. It could be confirmed that.

However, in the case of the etchant composition of Comparative Example 1 containing excessive hydrogen peroxide, the etching profile was very poor due to overetching of the Al-La-Ni thin film. In addition, in the case of the etching liquid composition of Comparative Example 2 containing an excessive amount of nitric acid, an etching profile defect and an underlying film damage due to overetching were observed. In the case of the etching liquid composition of Comparative Example 3 containing no fluorine-containing compound, unetching of the upper a-ITO occurred. In the case of the etchant composition of Comparative Example 4, the damage to the lower layer was very large due to the excess of the fluorine-containing compound. In addition, in the etching solution compositions of Comparative Example 5 and Comparative Example 6 containing no hydrogen peroxide or nitric acid, the etching rate was very slow and residues and poor etching profiles were observed.

Claims

Regarding the total weight of the composition,

1 to 15 weight percent hydrogen peroxide;

0.1 wt% to 10 wt% of an inorganic acid;

0.01 wt% to 5 wt% of a fluorine-containing compound; And

An etchant composition of a triple layer comprising an indium-based metal film, an aluminum-lanthanum-based alloy film, and a titanium-based metal film, including a residual amount of water.
The method according to claim 1, wherein the total weight of the composition,

2 to 12 weight percent hydrogen peroxide;

1 to 7 weight percent of inorganic acid;

0.1 wt% to 2 wt% of a fluorine-containing compound; And

An etchant composition of a triple layer comprising an indium-based metal film, an aluminum-lanthanum-based alloy film, and a titanium-based metal film, including a residual amount of water.
The method according to claim 1,

The inorganic acid is an etching liquid composition of a triple layer consisting of an indium-based metal film, an aluminum-lanthanum-based alloy film and a titanium-based metal film, characterized in that one selected from the group consisting of nitric acid, sulfuric acid and mixtures thereof.
The method according to claim 1,

The fluorine-containing compound is indium metal film, aluminum lanthanum-based, characterized in that one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride Etch liquid composition of a triple layer consisting of an alloy film and a titanium-based metal film.
The method according to claim 1,

The aluminum-lanthanum-based alloy film is an aluminum-lanthanum-based alloy film represented by Al-La or Al-La-X including 90 atomic% or more of aluminum, 10 atomic% or less of La, and the remaining amount of other metals X, wherein The other metal X is 1 selected from the group consisting of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt and C The etching liquid composition of the triple film | membrane which consists of an indium type metal film, an aluminum lanthanum type alloy film, and a titanium type metal film characterized by the above-mentioned, or 2 or more types.