KR20210088482A - Etching solution composition for indium oxide layer and manufacturing method of an array substrate for liquid crystal display using the same - Google Patents

Abstract

The present invention relates to an etching solution for an indium oxide film. More specifically, the present invention relates to: an etching solution for an indium oxide film which includes nitric acid and/or nitrous acid, a chlorine compound, a sulfate, a cyclic amine compound, phosphate, and water; and a method for manufacturing an array substrate for a liquid crystal display device using the same.

Description

Indium oxide film etchant composition and method for manufacturing an array substrate for liquid crystal display using the same

The present invention relates to an etchant composition of an indium oxide film and a method for manufacturing an array substrate for a liquid crystal display using the same.

In general, a thin film transistor (TFT) is used as a circuit board for independently driving each pixel in a liquid crystal display device, an organic electroluminescence (EL) display device, or the like. The thin film transistor array panel includes a scan signal line or gate line transmitting a scan signal, an image signal line or data line transmitting an image signal, and a thin film transistor connected to the gate line and the data line, and a thin film transistor connected to the thin film transistor. It consists of a pixel electrode and the like.

In manufacturing such a thin film transistor array panel, a process of laminating a metal layer for a gate wiring and a data wiring on a substrate and etching the metal layer to form a plurality of metal patterns is included. The metal layer is a single film made of copper or copper alloy, and further, two or more layers of copper or copper alloy/other metal, other intermetallic alloy, or metal oxide in order to reduce wiring resistance and increase adhesion with the silicon insulating film. The adoption of multiple membranes is being widely considered. For example, the copper/molybdenum film or the molybdenum/aluminum/molybdenum film may form the source/drain wiring constituting the gate wiring and the data line of the TFT-LCD, thereby contributing to a large screen size of the display.

After the metal pattern is formed, a pixel electrode layer connected to the thin film transistor is stacked, and a process of applying and patterning a photoresist is performed. The pixel electrode layer mainly uses indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), or gallium zinc indium oxide (IGZO), and the patterning process uses the photoresist as an anti-etching layer. It includes a process of patterning by performing etching with an etchant using an etchant. In such an etching process, a gate wire or a source or drain electrode that is in contact with or exposed to the pixel electrode layer may be damaged or deformed in the pixel electrode patterning process. Therefore, in order to improve this point, the material of the pixel electrode layer and the gate and source/drain electrodes should be different. In addition, the etchant composition used to form the pixel electrode through etching must have excellent etching power and residue prevention properties for the etched film, and at the same time, as described above, a copper film, a copper / molybdenum film, or a molybdenum / aluminum / molybdenum For a metal film used as a lower film, such as a film, properties that do not cause damage are required.

Korean Patent Laid-Open No. 10-2006-0050581 discloses an etchant composition containing sulfuric acid, nitric acid, or perchloric acid, but when the lower thin film contains copper, the surface of the lower thin film is damaged during pixel electrode patterning. have.

Korean Patent Laid-Open No. 10-2012-0093499 discloses a non-halogenated etchant composition comprising nitric acid, sulfuric acid, an ammonium compound, a cyclic amine compound, and water. However, there is a problem that the etchant composition of the above composition is not suitable because it has environmental disadvantages such as overloading wastewater treatment by including environmentally harmful substances such as sulfuric acid.

Accordingly, an etchant that exhibits excellent etching characteristics for an etch target film such as an indium oxide film used as a pixel electrode, prevents wiring loss due to over-etching, and does not cause damage to a metal film that can be used as a lower film composition is required. In addition, there is a need for an etchant composition that is environmentally advantageous by limiting the use of environmentally harmful substances such as sulfuric acid.

Republic of Korea Patent Publication No. 10-2006-0050581 Republic of Korea Patent Publication No. 10-2012-0093499

The present invention is to solve the problems of the prior art as described above,

It has an excellent indium oxide film etch rate and low metal attack, and has a small side etch change to maintain a constant etch profile and prevent over-etching, An object of the present invention is to provide an indium oxide film etchant composition having environmentally advantageous properties by limiting the amount and type of inorganic acid, and a method for manufacturing an array substrate for a liquid crystal display using the same.

The present invention is

with respect to the total weight of the composition,

2 to 10% by weight of at least one acid (A) selected from nitric acid and nitrous acid;

0.1 to 5 wt% of a chlorine compound (B);

0.1 to 5% by weight of sulfate (C);

0.1 to 5 wt% of a cyclic amine compound (D);

0.1 to 5% by weight of phosphate (E); and

It provides an indium oxide film etchant composition comprising the remaining amount of water (F).

Also, the present invention

a) forming a gate wiring on the substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming an oxide semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the oxide semiconductor layer; and

e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a liquid crystal display comprising:

It provides a method of manufacturing an array substrate for a liquid crystal display, wherein step e) comprises forming an indium oxide film on the substrate and etching the indium oxide film etchant composition of the present invention to form a pixel electrode.

The indium oxide film etchant composition of the present invention includes a limited amount of inorganic acid, provides environmentally advantageous advantages, has an excellent etching rate for the indium oxide film while preventing over-etching, and low damage to the underlying metal film can provide the advantage of having

In addition, the method for manufacturing an array substrate for a liquid crystal display using the etchant composition of the present invention has an excellent etching profile, and by forming a pixel electrode in which the size of the electrode is maintained above a certain level on the array substrate for a liquid crystal display, excellent It is possible to manufacture an array substrate for a liquid crystal display having driving characteristics.

1 is an SEM photograph of measuring a side etch distance after etching using an etchant composition.
As an SEM photograph showing the residue generation evaluation result of FIG. 2 , (a) is a photograph in which residue is generated in the a-ITO film, and (b) is a photograph in which residue is not generated in the a-ITO film.
3 is a SEM photograph showing a result of evaluation of damage occurrence of a copper (Cu) film. (a) is a photograph in which damage occurs, and (b) is a photograph in which damage occurs.
4 is a SEM photograph showing the damage generation evaluation result of the Mo/Al/Mo triple film, (a) is a damage occurrence photograph, (b) is a damage non-occurrence photograph.

The inventors of the present inventors have made diligent efforts to solve the problem of disposing of etchant waste and to improve the etching rate of the etched film and the protection of the lower metal film while preventing over-etching, including a limited amount of inorganic acids, chlorine compounds, phosphates, etc. The present invention was completed as an etchant composition comprising.

The present invention is

With respect to the total weight of the etchant composition,

2 to 10% by weight of at least one acid (A) selected from nitric acid and nitrous acid;

0.1 to 5 wt% of a chlorine compound (B);

0.1 to 5% by weight of sulfate (C);

0.1 to 5 wt% of a cyclic amine compound (D);

0.1 to 5% by weight of phosphate (E); and

It relates to an indium oxide film etchant composition comprising the remaining amount of water (F).

The indium oxide layer may be indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), or indium gallium zinc oxide (IGZO), but is not limited thereto.

Hereinafter, each component constituting the indium oxide film etchant composition of the present invention will be described. However, the present invention is not limited to these components.

(A) at least one acid selected from nitric acid and nitrous acid

_{Nitric acid (HNO 3} ) and/or nitrous acid (HNO ₂ ) contained in the indium oxide film etchant composition of the present invention is a main component for etching the indium oxide film, and prevents damage to the photoresist pattern used as the etch stop film of the indium oxide film, and , it plays a role in minimizing the generation of residues.

The at least one acid (A) selected from nitric acid and nitrous acid is preferably contained in an amount of 2 to 10 wt%, more preferably 5 to 10 wt%, based on the total weight of the etchant composition of the present invention. When the content is less than 2% by weight based on the above reference, the etching rate of the indium oxide film is not smoothly performed, so that the etching rate is reduced and the process time is increased. In addition, residues may be generated and etching may be incomplete in some areas. On the other hand, if it exceeds 10% by weight, the etching rate is increased, but it is difficult to control the etching, so over-etching may occur. In addition, an increase in the total nitrogen amount (Total N) causes a burden of treatment cost due to an increase in the amount of waste to be treated and may aggravate the environmental pollution problem, which is undesirable.

The content of nitric acid and/or nitrous acid may be appropriately adjusted according to the type and characteristics of the etch target layer.

(B) chlorine compound

The chlorine compound (B) included in the indium oxide film etchant composition of the present invention serves as an auxiliary etchant through the substitution reaction of the indium oxide film, serves to remove the etching residue, and is etched with nitric acid and / or nitrous acid It functions to control the etching rate of the film. Conventional etchant compositions generally contain sulfuric acid and thus have an excellent etching rate for the etched film, but by using a strong acid, there is an environmental disadvantage and damage to the photoresist when used with a strong acid such as nitric acid, resulting in damage to the indium oxide film. There was a problem of causing overeating. The indium oxide layer etchant composition of the present invention eliminates the use of sulfuric acid and limits the content of nitric acid and/or nitrous acid, and includes the chlorine compound, thereby maintaining etching performance and solving environmental problems.

The chlorine compound included in the etchant composition of the present invention is not particularly limited, but at least one selected from hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH ₄ Cl), etc. may be used. .

The chlorine compound is preferably contained in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of the etchant composition. If the content of the chlorine compound is less than 0.1 wt %, it is difficult to exhibit excellent etch rate performance for the indium oxide layer, and residue generation and etching failure may occur. On the other hand, when the content of the chlorine compound exceeds 5% by weight, over-etching of the pixel electrode occurs due to an increase in the etch rate, which makes it difficult to form an area for sufficiently driving the pixel electrode. In addition, it is not appropriate because it causes damage to metal films such as copper (Cu), aluminum (Al), molybdenum (Mo) or titanium (Ti) that can be used as a lower layer, and the limited use of chlorine compounds is important is required to

That is, when the content of the chlorine compound satisfies the above range, it is preferable because over-etching and etching residues are prevented and damage to the glass substrate or the lower metal layer is not caused.

(C) sulfate

The sulfate (C) contained in the indium oxide film etchant composition of the present invention serves to prevent damage to the lower metal film such as copper, aluminum, or molybdenum. That is, the nitric acid and/or nitrous acid, and the chlorine compound serve as a corrosion inhibitor to prevent damage to the film under the indium oxide film.

In the present invention, the type of the sulfate (C) is not particularly limited, ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), ammonium sulfide ((NH ₄ ) ₂ S), sodium sulfate (Na ₂ SO ₄ ), potassium sulfate (K ₂ SO ₄₎ and the like, may be used one or more selected therefrom.

The sulfate (C) is preferably included in an amount of 0.1 to 5 wt%, more preferably 0.5 to 3 wt%, based on the total weight of the etchant composition of the present invention. When the sulfate is contained in an amount of less than 0.1 wt%, it is difficult to expect the effect of preventing corrosion of metal films such as copper (Cu), aluminum (Al), molybdenum (Mo), titanium (Ti), which can be used as a lower film, and it is preferable. don't In this case, there is a method of lowering the amount of the chlorine compound to prevent damage to the metal film, but this is not appropriate because it may increase the residue generation rate after etching the indium oxide film. On the other hand, when the sulfate is contained in excess of 5% by weight, the corrosion-preventing effect of the lower layer is high, but the etching rate of the indium oxide layer using the etchant, which was the original purpose, is lowered, so that the process time may be lengthened, and the defect phenomenon of residues occurring can cause

(D) cyclic amine compounds

The cyclic amine compound (D) included in the indium oxide film etchant composition of the present invention serves to prevent damage to the lower metal film such as copper, aluminum, or molybdenum. That is, like the sulfate, the nitric acid and/or nitrous acid, and the chlorine compound serve to prevent damage to the film under the indium oxide film.

The type of the cyclic amine compound (D) of the present invention is not particularly limited, and specific examples thereof are preferably pyrrole, pyrazole, imidazole, and triazole. and tetrazole, pentazole, oxazole, isoxazole, thiazole, and isothiazole. , at least one selected from these may be used. More preferably, benzotriazole as a triazole type; 5-aminotetrazole, 3-aminotetrazole, and 5-methyltetrazole as tetrazoles; and at least one selected from among them. Among these, benzotriazole is more preferable.

The cyclic amine compound (D) is preferably included in an amount of 0.1 to 5 wt%, more preferably 0.5 to 2 wt%, based on the total weight of the etchant composition of the present invention. When the cyclic amine compound is included in less than 0.1% by weight, it reduces damage to a metal film such as copper (Cu), aluminum (Al), molybdenum (Mo), titanium (Ti), which can be used as a lower film. It is not preferable because the effect is difficult to expect. On the other hand, when the cyclic amine compound is included in an amount exceeding 5 wt %, the etching rate of the indium oxide film using the etchant may be lowered, thereby increasing the process time.

(E) phosphate

Phosphate (E) contained in the indium oxide film etchant composition of the present invention reduces the side etch distance for the thin film during wet etching, and prevents over-etching and uniformity by preventing an increase in the amount of lateral etching according to the increase of the etching time. It functions to be etched.

Conventionally, the indium oxide film forming the pixel electrode was used with a thickness of 50 nm or less, but it tends to be thicker than 100 nm according to the demand for a fast response speed and high resolution of a display. As the thickness of the indium oxide layer increases, the etching time for etching the indium oxide layer increases, and the amount of etching in the longitudinal direction as well as the transverse direction increases, resulting in an over-etching problem. For this reason, there is a problem in that it is difficult to apply the miniaturized wiring for realizing high resolution. The phosphate reduces the amount of side etch and serves to improve the amount of one-sided etch that may occur due to an increase in the etching time, that is, the over-etching phenomenon in the lateral direction.

The phosphate salt is, as an example, sodium phosphate monobasic (NaH ₂ PO ₄ ), sodium phosphate dibasic (Na ₂ HPO ₄ ), sodium phosphate tribasic (Na ₃ PO ₄ ), potassium phosphate monobasic (KH ₂ PO ₄ ), Potassium phosphate dibasic (K ₂ HPO ₄ ), ammonium phosphate monobasic ((NH ₄ )H ₂ PO ₄ ), ammonium phosphate dibasic ((NH ₄ ) ₂ HPO ₄ ) and ammonium tertiary phosphate ((NH ₄ ) _{3 )} PO ₄ ) and the like, but is not limited thereto, and one or more selected from them may be used.

The phosphate (E) may be included in an amount of 0.1 to 5% by weight, more preferably 0.5 to 2% by weight, based on the total weight of the etchant composition of the present invention. When the content of the phosphate is less than 0.1 wt %, it is difficult to apply to the formation of fine wiring due to the decrease in etch uniformity in the substrate or the increase in side etch. If the content exceeds 5% by weight, the etching rate of the indium oxide film is lowered by more than 10 times, so that the desired etching rate cannot be realized. have.

(F) water

The indium oxide film etchant composition of the present invention includes water (F) in addition to nitric acid and/or nitrous acid, a chlorine compound, a sulfate, a cyclic amine compound, and a phosphate. The water is not particularly limited, but it is preferable to use deionized water, and it is preferable to use it for semiconductor processing. It may be more preferable that the water has a specific resistance value of 18 ㏁/cm or more.

The water may be included in the remaining amount based on 100% by weight of the total etchant composition.

The indium oxide film etchant composition of the present invention may further include at least one selected from an etch control agent, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH control agent, and other additives, but not limited thereto, in addition to the above-mentioned components. have. The additive may be selected from additives commonly used in the art in order to further improve the effects of the present invention within the scope of the present invention.

The components constituting the indium oxide film etchant composition of the present invention preferably have a purity for semiconductor processing.

As a specific example of the indium oxide film etched by the indium oxide film etchant composition of the present invention, indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), indium gallium zinc oxide (IGZO), etc. One or more types may be mentioned, but the present invention is not limited thereto. The indium oxide layer may be in a crystalline state or an amorphous state, and when the indium oxide film is in the amorphous state, it may be crystallized by heat treatment.

The indium oxide film etchant composition of the present invention is characterized in that it does not cause damage to the lower film of the indium oxide film. The type of the lower film is not particularly limited, but as a specific example, a lower film including a copper-based metal film, a molybdenum-based metal film, an aluminum-based metal film, a titanium-based metal film, or a multilayer film made of these may be mentioned. It can be used more preferably.

The copper-based metal film means a copper film or a copper alloy film, the molybdenum-based metal film means a molybdenum film or a molybdenum alloy film, the aluminum-based metal film means an aluminum film or an aluminum alloy film, and the titanium-based metal film is a titanium film or It means a titanium alloy film.

The multilayer film may include, for example, a double film of a molybdenum-based metal film/copper-based metal film having a copper-based metal film as a lower film and a molybdenum-based metal film as an upper film; A copper-based metal film/molybdenum-based metal film having a molybdenum-based metal film as a lower film and a copper-based metal film as an upper film, a double film of a copper-based metal film/molybdenum-titanium-based metal film, and a molybdenum-based metal film/copper-based metal and a triple or more multilayer film in which a copper-based metal and a molybdenum-based metal film are alternately stacked, such as a film/molybdenum-based metal film, or a copper-based metal film/molybdenum-based metal film/copper-based metal film.

In addition, the multilayer film is, for example, a double film of a titanium-based metal film/copper-based metal film in which a copper-based metal film is a lower film and a titanium-based metal film is an upper film, a titanium-based metal film is a lower film and a copper-based metal film is an upper film a copper-based metal film/titanium-based metal film, and a copper-based metal and titanium-based film, such as a titanium-based metal film/copper-based metal film/titanium-based metal film or a copper-based metal film/titanium-based metal film/copper-based metal film It includes a multilayer film of three or more layers in which metal films are alternately stacked.

In addition, the multilayer film is, for example, a double film of a molybdenum-based metal film/aluminum-based metal film having an aluminum-based metal film as a lower film and a molybdenum-based metal film as an upper film, a molybdenum-based metal film as a lower film and an aluminum-based metal film as an upper film A double film of an aluminum-based metal film/molybdenum-based metal film, and a triple film or more in which a titanium-based metal film/aluminum-based metal film/titanium-based metal film or an aluminum-based metal film/titanium-based metal film/aluminum-based metal film are alternately stacked includes multiple membranes.

In the multilayer film, the interlayer bonding structure may be determined by considering a material constituting the film disposed on the upper or lower portion of the multilayer film, or adhesion with the films.

In the above, the copper, molybdenum, aluminum or titanium alloy film means a metal film made of an alloy using copper, molybdenum, aluminum or titanium as a main component and other metals according to the characteristics of the film. For example, the molybdenum alloy film has molybdenum as a main component and is formed by including one or more selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In). It means a film made of an alloy.

The indium oxide film etchant composition of the present invention is, in particular, a copper-based metal film, a copper-based metal film/molybdenum-based metal film, a titanium-based metal film/copper-based metal film, or a molybdenum-based metal film/aluminum-based metal film/molybdenum-based metal film. It can be preferably used for etching an indium oxide film having as a film. However, the use of the indium oxide film etchant composition is not limited to the metal film.

Also, the present invention

a) forming a gate wiring on the substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming an oxide semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the oxide semiconductor layer; and

e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a liquid crystal display comprising:

It provides a method of manufacturing an array substrate for a liquid crystal display, wherein step e) comprises forming an indium oxide film on the substrate and etching the indium oxide film etchant composition of the present invention to form a pixel electrode.

The indium oxide layer may include, but is not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), and indium gallium zinc oxide (IGZO).

Step a) may include forming a metal film on a substrate and etching the metal film to form a gate wiring,

Step d) may include forming a metal film on the oxide semiconductor layer, and etching the metal film to form source and drain electrodes,

The etching of the metal film in step a) or d) may be performed using an appropriate metal film etchant composition in addition to the indium oxide film etchant composition of the present invention.

The array substrate for the liquid crystal display may be a thin film transistor (TFT) array substrate.

In addition, the present invention provides an array substrate for a liquid crystal display device manufactured by the method of manufacturing the array substrate for a liquid crystal display device.

Also, the present invention

An etched wiring may be provided using the indium oxide layer etchant composition of the present invention. In more detail, the wiring may be a touch sensing wiring that mainly forms X and Y axis coordinates in a touch screen panel (TSP).

As an example, a touch screen panel may be manufactured by depositing an ITO layer on one surface of one base substrate and etching the X and Y-axis wires on the ITO layer.

As another example, a touch screen panel can be manufactured by depositing an ITO layer on both sides of the base substrate and patterning the ITO layer by etching the X and Y-axis wires, respectively.

The etching may be performed using the indium oxide film etchant composition of the present invention.

The wiring may be an indium oxide film, and more specifically, at least one selected from indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), and indium gallium zinc oxide (IGZO). , but the present invention is not limited thereto. The indium oxide layer may be in a crystalline state or an amorphous state.

As described above, by using the indium oxide film etchant composition of the present invention, the metal oxide film containing indium can be effectively controlled and etched, and corrosion and damage to the lower wiring can be prevented. In addition, the indium oxide film etchant composition of the present invention may be used not only in the manufacture of flat panel displays such as liquid crystal displays, but also in the manufacture of organic light emitting devices (OLEDs), touch screens, and memory semiconductor panels. In addition, it can be used in the manufacture of other electronic devices including a metal oxide film wiring made of a single film in which a metal oxide film containing indium is formed.

Hereinafter, the present invention will be described in more detail using examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples, and may be appropriately modified and changed by those skilled in the art within the scope of the present invention. The scope of the present invention will be determined by the technical spirit of the claims to be described later.

<Examples and Comparative Examples> Preparation of etchant composition

Etching liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were prepared with the compositions and contents shown in Table 1 below.

Item Etch solution composition (wt%) nitric acid or
nitrite chlorine compound sulfate annular
Mineral compounds phosphate deionized water nitric acid nitrite chloride
salt chloride
potassium chloride
ammonium sulfuric acid
ammonium sulfuric acid
salt benzo
triazole 5-amino
tetrazole phosphoric acid
salt phosphoric acid
ammonium Example 1 7 - 2 - - 2 - 0.5 - 2 - remaining amount Example 2 9 - 5 - - 5 - 5 - 5 - Example 3 5 - 2 - - 0.5 - 0.5 - 0.5 - Example 4 2 - 2 - - 2 - 0.5 - 2 - Example 5 2 0.1 - - 3 - 3 - 3 - Example 6 - 7 2 - - 2 - 0.5 - 2 - Example 7 7 - - - 2 - 2 - 2 2 - Example 8 7 - - 2 - - 2 0.5 - - 2 Example 9 7 - 2 - 2 - - 0.5 2 - Comparative Example 1 11 - 2 - - 2 - 0.5 - 2 - Comparative Example 2 7 - 6 - - 2 - 0.5 - 2 - Comparative Example 3 7 - 2 - - 6 - 0.5 - 2 - Comparative Example 4 7 2 - - 2 - 6 - 2 - Comparative Example 5 7 - 2 - - 2 - 0.5 - 6 - Comparative Example 6 7 - 2 - - - - 0.5 - 2 - Comparative Example 7 7 - 2 - - 2 - - - 2 - Comparative Example 8 7 - 2 - - 2 - 0.5 - - - Comparative Example 9 One - 2 - - 2 - 0.5 - 2 - Comparative Example 10 7 - - - - 2 - 0.5 - 2 -

<Experimental example> Experimental Example 1. Evaluation of one-sided etching of the etchant composition

A single a-ITO film was deposited on a glass substrate (100 mm X 100 mm). Thereafter, a sample in which a photoresist having a predetermined pattern was formed was manufactured through a photolithography process.

An etching process was performed on the sample using each of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10. Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the etchant composition during the etching process was set to 40 ° C. When the temperature reached 40 ± 0.1 ° C., the etching process of the specimen The a-ITO film was etched for 60 seconds. After washing and drying, the length of the side etch was checked using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), and the results are shown in Table 2 below.

<Side Etch Evaluation Criteria>

◎ (Excellent): less than 0.2㎛

○ (Good): Less than 0.2 ~ 0.5㎛

X (defective): 0.5㎛ or more

Experimental Example 2. Measurement of residue

A single a-ITO film was deposited on a glass substrate (100 mm X 100 mm). Thereafter, a sample in which a photoresist having a predetermined pattern was formed was manufactured through a photolithography process.

Each of the silver etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), KCTech), and the temperature was set to 40 ° C. When the temperature reached 40±0.1° C., the etching process of the sample was performed. The total etching time was set to 60 seconds.

After inserting the substrate and starting spraying, when the etching time of 60 seconds is over, it is taken out, washed with deionized water, dried using a hot air dryer, and the photoresist is removed using a photoresist stripper (PR stripper). After washing and drying, the residue, a phenomenon in which the ITO film is not etched, was measured on the part not covered with the photoresist using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), and evaluated according to the following criteria. Thus, the results are shown in Table 2 below.

<Residue Evaluation Criteria>

○ (Good): No residue

X (defective): residue generation

Experimental Example 3. Evaluation of metal damage of the etchant composition

A single film of a copper (Cu) metal film or a triple film of a molybdenum metal film/aluminum metal film/molybdenum metal film (Mo/Al/Mo) was deposited on a glass substrate (100 mm×100 mm). Thereafter, a sample in which a photoresist having a predetermined pattern was formed was manufactured through a photolithography process.

After forming the metal wiring through an etchant suitable for the metal film, the photoresist was completely removed through a stripping process using a stripper, leaving only the metal film wiring.

Using each of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10, the samples were subjected to the same conditions as the etching process for 10 minutes. Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the etching solution composition during the etching process was about 40°C. In order to evaluate the degree of damage to the lower membrane, it was examined using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), and the results are shown in Table 2 below.

<Lower membrane damage evaluation criteria>

○ Good: (thickness, width, etc.) damage less than 0.1㎛,

X Defect: (thickness, width, etc.) damage 0.1㎛ or more

Item one-sided etch distance residue lower membrane damage Cu Mo, Al Example 1 ◎ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 ◎ ○ ○ ○ Example 4 ◎ ○ ○ ○ Example 5 ◎ ○ ○ ○ Example 6 ◎ ○ ○ ○ Example 7 ◎ ○ ○ ○ Example 8 ◎ ○ ○ ○ Example 9 ◎ ○ ○ ○ Comparative Example 1 X ○ ○ ○ Comparative Example 2 X ○ X X Comparative Example 3 ○ X ○ ○ Comparative Example 4 ○ X ○ ○ Comparative Example 5 ◎ X ○ ○ Comparative Example 6 ◎ ○ ○ X Comparative Example 7 ◎ ○ X ○ Comparative Example 8 X ○ ○ ○ Comparative Example 9 ◎ X ○ ○ Comparative Example 10 ◎ X ○ ○

The etching characteristics and lower metal film damage of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were evaluated. As can be seen through Examples 1 to 9 described in Table 1, in the side etch evaluation, the side etch length was excellent at less than 0.2 μm or at a good level of less than 0.5 μm, so it was confirmed that it was a level suitable for mass production. The etchant compositions of Examples 1 to 9 did not leave a residue, and damage to copper, molybdenum, and aluminum metal did not occur. On the other hand, in the case of the comparative example, it was not suitable for mass production from the side etch evaluation results. It showed a result of 0.5 μm or more, which is an unsatisfactory level (Comparative Examples 1, 2, and 8), and residues were generated (Comparative Examples 3, 4, 5, 9 and 10), or damage to the copper, molybdenum, and aluminum metals as the lower layer was generation (Comparative Examples 2, 6 and 7) gave poor results.

That is, the indium oxide film etchant composition of the present invention not only has an environmentally advantageous aspect because it does not use a harmful substance such as sulfuric acid, but also has excellent etching properties and metal damage prevention properties without containing sulfuric acid. It was confirmed that the composition has different advantages.

Claims (12)

relative to the total weight of the composition,
2 to 10% by weight of at least one acid (A) selected from nitric acid and nitrous acid;
0.1 to 5 wt% of a chlorine compound (B);
0.1 to 5% by weight of sulfate (C);
0.1 to 5 wt% of a cyclic amine compound (D);
0.1 to 5% by weight of phosphate (E); and
Including the remaining amount of water (F),
The chlorine compound (B) is sodium chloride (NaCl),
The sulfate (C) is at least one selected from ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ) and potassium sulfate (K ₂ SO ₄ ),
The phosphate (E) is monobasic sodium phosphate (NaH ₂ PO ₄ ), dibasic sodium phosphate (Na ₂ HPO ₄ ), trisodium phosphate (Na ₃ PO ₄ ), monobasic potassium phosphate (KH ₂ PO ₄ ), Potassium phosphate dibasic (K ₂ HPO ₄ ), ammonium phosphate monobasic ((NH ₄ )H ₂ PO ₄ ), ammonium phosphate dibasic ((NH ₄ ) ₂ HPO ₄ ) and ammonium tertiary phosphate ((NH ₄ ) _{3 )} PO ₄ ) Indium oxide film etchant composition, characterized in that at least one selected from the group consisting of.
The method according to claim 1,
The cyclic amine compound (D) is a pyrrole-based, pyrazole-based, imidazole-based, triazole-based, tetrazole-based, pentaazole-based, Indium oxide film etchant composition, characterized in that at least one selected from oxazole-based, isoxazole-based, diazole-based and isothiazole-based compounds.
The method according to claim 1,
The indium oxide film is an indium oxide film etchant composition, characterized in that at least one selected from indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO) and indium gallium zinc oxide (IGZO).
The method according to claim 1,
An indium oxide film etchant composition for preventing damage to copper, molybdenum and aluminum metal.
The method according to claim 1,
The chlorine compound (B) is based on the total weight of the composition,
Indium oxide film etchant composition comprising 0.5 to 3% by weight.
a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming an oxide semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the oxide semiconductor layer; and
e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a liquid crystal display comprising:
The method for manufacturing an array substrate for a liquid crystal display, wherein step e) comprises forming an indium oxide film on the substrate and etching the indium oxide film etchant composition according to claim 1 to form a pixel electrode.
7. The method of claim 6,
The method of manufacturing an array substrate for a liquid crystal display, characterized in that the array substrate for the liquid crystal display is a thin film transistor (TFT) array substrate.
An array substrate for a liquid crystal display device manufactured by the manufacturing method of any one of claims 6 to 7.
The wiring etched with the indium oxide film etchant composition of any one of claims 1 to 5. 10. The method of claim 9,
The wiring is a wiring, characterized in that the touch sensing wiring for a touch screen panel (TSP).
10. The method of claim 9,
The wiring is an indium oxide film.
12. The method of claim 11,
The indium oxide layer is at least one selected from indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), and indium gallium zinc oxide (IGZO).

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