KR20180130183A - Etchant composition for etching metal layer and method of forming conductive pattern using the same - Google Patents

Abstract

According to an embodiment of the present invention, provided is an etchant composition for etching a metal layer, which comprises: 35-70 wt% of an organic oxidizing agent; 1-10 wt% of an etching enhancing agent having an inorganic acid; and extra water. The etchant composition for etching a metal layer is used to form a conductive pattern in which an etching defect is reduced.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal film etchant composition and a conductive pattern forming method using the metal film etchant composition.

The present invention relates to a metal film etchant composition and a method for forming a conductive pattern using the same. More particularly, the present invention relates to a metal film etchant composition containing an acid component and a method of forming a conductive pattern using the same.

For example, a thin film transistor (TFT) is used as a part of a driving circuit of a semiconductor device and a display device. The TFT is arranged for each pixel on a substrate of, for example, an organic light emitting display (OLED) device or a liquid crystal display device (LCD), and is connected to a pixel electrode, a counter electrode, a source electrode, a drain electrode, May be electrically connected to the TFT.

In order to form the electrode or the wiring, a metal film may be formed on a display substrate, a photoresist may be formed on the metal film, and then the metal film may be partially removed using an etchant composition.

The metal film may be formed of a multi-layered film containing dissimilar metals having different chemical properties, or a different kind of conductive material, in order to prevent the signal transmission delay by reducing the wiring resistance and ensure the chemical resistance and stability of the wiring.

For example, a transparent conductive oxide film such as indium tin oxide (ITO) may be additionally formed for forming a silver (Ag) -containing film and improving chemical resistance, stability, and transparency for realizing a low resistance property .

As described in Korean Patent Registration No. 10-0579421, an inorganic acid strong acid such as phosphoric acid, nitric acid, sulfuric acid and the like is used as a base component of the etchant composition. However, when inorganic strong acid is used, non-uniform etching profile, over-etch, and over-hang due to different etching rates of different conductive films may be caused.

Korean Patent Registration No. 10-0579421 (2006.05.08.)

An object of the present invention is to provide a metal film etchant composition having improved etching uniformity and reliability.

One aspect of the present invention is to provide a method for forming a conductive pattern using the metal film etchant composition.

1. 35 to 70% by weight of an organic oxidant, based on the total weight of the composition; 1 to 10% by weight of an etching enhancer comprising an inorganic acid; And an excess of water.

2. The composition of claim 1 wherein said organic oxidant is selected from the group consisting of methanesulfonic acid, glycolic acid, formic acid, malonic acid, citric acid, lactic acid, malic acid, gluconic acid, sulfamic acid, para toluenesulfonic acid, iminodiacetic acid, oxalic acid, tartaric acid and ascorbic acid Wherein at least one of the metal film etchant composition and the metal film etchant composition comprises at least one selected from the group.

3. The metal film etchant composition of 1 above, wherein the etch enhancer comprises at least one of nitric acid or sulfuric acid.

4. The metal film etchant composition of 1 above, wherein the metal film comprises a silver-containing film.

5. The metal film etchant composition of 4 above, wherein the metal film further comprises a transparent conductive oxide film.

6. The metal film etchant composition of 5 above, wherein the transparent conductive oxide film comprises a first transparent conductive oxide film and a second transparent conductive oxide film formed with the silver-containing film therebetween.

7. The transparent conductive oxide film of claim 5, wherein the transparent conductive oxide film is made of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium zinc oxide (GZO) and indium gallium zinc oxide (IGZO) Wherein at least one of the metal film etchant composition and the metal film etchant composition comprises at least one selected from the group.

8. The metal film etchant composition of any preceding claim, which does not comprise phosphoric acid or phosphoric acid based compounds.

9. The composition of claim 1, wherein from 40 to 60% by weight of the total weight of the composition of the organic oxidant; 5 to 10% by weight of the etch enhancer; And an excess of water.

10. forming a metal film on a substrate; And etching the metal film using any one of the metal film etching solution compositions 1 to 9 above.

11. The method of forming a conductive pattern according to claim 10, wherein the step of forming the metal film includes the step of forming a silver-

12. The method of forming a conductive pattern according to claim 11, wherein the forming of the metal film further comprises forming a transparent conductive oxide film.

13. The method of forming a conductive pattern according to claim 10, further comprising the step of tilting the substrate on which the metal film is formed.

14. The method of claim 10,

Forming a thin film transistor on the substrate;

Forming a pixel electrode electrically connected to the thin film transistor; And

Forming a display layer on the pixel electrode,

Wherein the metal film is formed on the display layer.

15. The conductive pattern forming method according to 14 above, wherein the conductive pattern is provided as a common electrode, a reflective electrode or a wiring of an image display apparatus.

16. The method of claim 14, wherein the conductive pattern is provided as a trace or sensing electrode of a touch sensor.

The etchant composition according to the embodiments of the present invention described above may include an organic oxidizing agent as a base material. Therefore, it is possible to prevent over-etching and tip phenomenon of a metal film (for example, a silver-containing film) due to the use of strong acid such as phosphoric acid.

In addition, as the content of strong acid such as phosphoric acid, sulfuric acid, etc. is excluded or reduced, it is possible to prevent damage to other substructures other than the film to be etched.

In addition, when the metal film further includes a transparent conductive oxide film, the organic oxidizing agent is used as a main etching agent, for example, the difference in etching rate between the silver-containing film and the transparent conductive oxide film is reduced, The continuity and the uniformity of the film can be improved.

For example, an electrode or wiring such as a reflection electrode of an image display device, a sensing electrode of a touch sensor, a trace, a pad, or the like can be formed to have a desired aspect ratio and profile by using the above etching composition.

1 and 2 are schematic cross-sectional views for explaining a conductive pattern forming method according to exemplary embodiments.
3 is a schematic sectional view showing a conductive pattern shape formed according to a comparative example.
4 is a schematic cross-sectional view for explaining a conductive pattern forming method according to exemplary embodiments.
5 is a schematic cross-sectional view illustrating an image display device manufactured in accordance with some exemplary embodiments.
Figure 6 is a schematic plan view illustrating a touch sensor fabricated in accordance with some exemplary embodiments.

According to embodiments of the present invention, a metal film etchant composition (hereinafter abbreviated as "etchant composition") comprising an organic oxidizing agent, an etch enhancer, and water is provided. Further, a method of forming a conductive pattern using the metal film etchant composition is provided.

The term "metal film" used in the present application is used as a term encompassing a metal single film and a laminated structure of the metal single film and the transparent conductive oxide film. In addition, the metal film may include a plurality of single metal films formed of different metals.

In exemplary embodiments, the metal film may comprise a silver containing film. The silver containing film may refer to a film comprising silver or a silver alloy. Further, the silver-containing film may include a multilayer structure of two or more layers.

For example, the silver alloy may be at least one selected from the group consisting of neodymium (Nd), copper (Cu), palladium (Pd), niobium (Ni), nickel (Ni), molybdenum (Mo), chromium (Cr), magnesium (W), protactinium (Pa), titanium (Ti) or a combination of two or more thereof and an alloy of silver (Ag); A silver compound containing dopant elements such as nitrogen (N), silicon (Si), and carbon (C); Or a combination of two or more thereof.

The transparent conductive oxide may include a transparent metal oxide. For example, the transparent metal oxide may be selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium zinc oxide (GZO), indium gallium zinc oxide (IGZO) .

Hereinafter, embodiments of the present invention will be described in detail and a case where the metal film includes a silver-containing film and a transparent conductive oxide film will be described as an example. However, this is a preferable example, and the spirit and scope of the present invention are not necessarily limited thereto.

≪ Etchant composition &

The organic oxidizer included in the etching solution composition according to embodiments of the present invention may be included as a main etching agent or a main oxidizing agent for metal film oxidation or dissociation. According to exemplary embodiments, the organic oxidant may be the most abundant component of the etchant composition except for water.

The organic oxidizing agent may be provided as a component that implements a wet etching process by oxidizing or dissociating the silver containing film. According to exemplary embodiments, the organic oxidizing agent is selected from the group consisting of methanesulfonic acid, glycolic acid, formic acid, malonic acid, citric acid, lactic acid, malic acid, gluconic acid, sulfamic acid, para toluenesulfonic acid, iminodiacetic acid, oxalic acid, tartaric acid, ascorbic acid . ≪ / RTI > In one embodiment, it may be advantageous to include methanesulfonic acid in terms of etch rate.

In some embodiments, the organic oxidant may be included in an amount of about 35-70 wt% of the total weight of the composition. If the content of the organic oxidizing agent is less than about 35% by weight, a sufficient etching ability may not be secured, thereby reducing the number of treatments in the silver residue and etching process. When the content of the organic oxidizing agent is more than about 70% by weight, overexposure of the silver-containing film may occur and tip phenomenon may occur in the etching region of the transparent conductive oxide film.

In one embodiment, the content of the organic oxidizing agent may be adjusted to about 40 to 60% by weight considering the uniform etching rate of the silver-containing film and the transparent conductive oxide film.

The etchant compositions in accordance with exemplary embodiments can include an etch enhancer that includes inorganic acids. The etch enhancer may be provided as a component for supplementing the etch rate in the wet etch process proceeding through the organic oxidant. In addition, it can be included as a component for promoting etching by inducing a substitution reaction on a transparent conductive oxide film having a relatively low oxidation / reduction characteristic compared to silver.

The etch enhancer may include, for example, nitric acid and / or sulfuric acid. In one embodiment, nitric acid is used as the etch enhancer, and sulfuric acid, if used, may be used together as an auxiliary component of the nitric acid.

In some embodiments, the etch enhancer may be included in an amount of about 1 to 10 wt% of the total weight of the composition. If the content of the etching promoter is less than about 1 wt%, the etching rate may be excessively reduced, resulting in a wiring short due to silver residue. Also, dark spots or blind spots may occur due to the silver residue. If the content of the etching promoter exceeds about 10% by weight, the main oxidizing agent action of the organic oxidizing agent may be inhibited, and etching control failure of the metal film such as an overexposure angle may occur.

In one embodiment, the content of the etching enhancer may be adjusted to about 5 to 10% by weight in consideration of the uniform etching rate of the silver-containing film and the transparent conductive oxide film.

The etchant composition may include excess or residual water except for the organic oxidizing agent and the etch enhancer, and may include deionized water, for example. In the case of the deionized water, for example, it may have a resistivity value of 18 M? / Cm or more.

The term "extra or residual amount " as used in the present application means a variable amount including the amounts excluding the organic oxidant, the etch enhancer and the additive, when other additives are included.

In some embodiments, the additive may be included to improve etch efficiency or etch uniformity to the extent that it does not interfere with the action of the organic oxidant and / or etch enhancer described above. For example, the additives may include anti-corrosive agents, pH adjusting agents, anti-adsorption of etching by-products, agents for adjusting the taper angle of an etching pattern, and the like widely used in the art.

In some embodiments, the etchant composition may not comprise phosphoric acid or phosphoric acid based compounds (e.g., phosphates). In the case of the phosphoric acid or phosphoric acid-based compound, loss due to overgrowth of the metal film, damage to the lower structure, and re-adsorption may occur. In addition, in the case of the phosphoric acid or phosphoric acid compound, the viscosity of the etching solution composition may be excessively increased to cause an etching deviation in each region of the etching target film.

However, the etchant composition can eliminate the phosphoric acid or the phosphoric acid-based compound and improve the etch uniformity while preventing the over-eating angle of the silver-containing film as the organic oxidant is used as each component of the stock.

In some embodiments, the viscosity of the etchant composition can be about 1.2 to 3.0 cp (e. G., At 25 ^° C). Since the etchant composition has a relatively reduced viscosity, the fluidity of the composition is improved, and an increase in etching variation due to dipping of the etch target can be suppressed.

In some embodiments, too strong oxidants such as peroxide series such as hydrogen peroxide, chloric acid series (HClO ₂ , HClO ₄ , HClO _3, etc.), iodic acid series (HIO _4, etc.) Can be excluded from the etchant composition. When the above-described strong oxidizing agents are included, the etching rate of the silver-containing film and the transparent conductive oxide film may be excessively increased to hinder the action of the organic oxidizing agent.

As described above, the etchant composition according to the exemplary embodiments includes an organic oxidant as a main etchant, and can be efficiently utilized for etching a laminated structure of, for example, a silver-containing film or a silver-containing film / a transparent conductive oxide film . By the organic oxidizing agent, it is possible to prevent over-etching, damage and re-adsorption of the silver-containing film having a large ionization tendency, and to form a pattern having an excellent etching profile and etching uniformity without damaging the lower wiring or the lower conductive pattern. In addition, a relatively low-viscosity etching composition may be implemented to reduce etching variations due to dipping.

<Conductive Pattern Forming Method>

1 and 2 are schematic cross-sectional views for explaining a wiring forming method according to exemplary embodiments.

Referring to FIG. 1, a lower conductive pattern 115 and a lower insulating layer 110 may be formed on a substrate 100.

The substrate 100 may include a glass substrate, a polymer resin or a plastic substrate, an inorganic insulating substrate, or the like.

The lower conductive pattern 115 includes a transparent conductive oxide such as aluminum (Al), copper (Cu), molybdenum (Mo), tungsten (W), titanium (Ti), tantalum . The lower insulating film 110 may be formed to include an organic insulating material such as acrylic resin, polysiloxane, and the like, and / or an inorganic insulating material such as silicon oxide, silicon nitride, silicon oxynitride, and the like.

The lower conductive pattern 115 may be provided, for example, as a conductive via or a conductive contact.

According to exemplary embodiments, the first transparent conductive oxide film 121, the silver-containing film 123, and the second transparent conductive oxide film 125, which are sequentially stacked on the lower insulating film 110 and the lower conductive pattern 115, The metal film 120 can be formed. Accordingly

The first and second transparent conductive oxide films 121 and 125 may be formed to include a transparent metal oxide such as ITO, IZO, GZO, IGZO, or the like. The silver containing film 123 may be formed to include a silver and / or silver alloy as described above. The first transparent conductive oxide film 121, the silver containing film 123 and the second transparent conductive oxide film 125 may be formed through a deposition process such as a sputtering process.

A mask pattern 130 may be formed on the metal film 120. For example, after the photoresist film is formed on the second transparent conductive oxide film 125, the photoresist film may be partially removed through the exposure and development processes to form the mask pattern 130.

Referring to FIG. 2, the metal film 120 may be etched using the metal film etchant composition according to the above-described exemplary embodiments to form the conductive pattern 120a. The conductive pattern 120a includes a first transparent conductive oxide film pattern 122, a silver-containing pattern 124 and a first transparent conductive oxide film pattern 126 which are sequentially stacked on the lower insulating film 110 .

The conductive pattern 120a can be utilized, for example, as a pad, an electrode, or a wiring of an image display apparatus. By forming the relatively silver-containing pattern 124 having a low resistance and a good signal transmission property between the first and second transparent conductive oxide film patterns 122 and 126 having excellent corrosion resistance, a low resistance and mechanical and chemical reliability An improved conductive pattern can be realized.

Also, as the etchant composition including the organic oxidant and the etch enhancer is utilized and the amount of strong acid such as phosphoric acid is eliminated or reduced, the overgrowth of the silver containing pattern 124 is prevented, and a substantially uniform and continuous sidewall profile The conductive pattern 120a may be formed.

In some embodiments, the thickness of the silver containing film 123 or the silver containing pattern 124 may be at least about 800 A, and in one embodiment at least about 1000 A. The thickness of the first and second transparent conductive oxide film patterns 122 and 126 may be about 50 to 100 ANGSTROM.

As the thickness of the silver-containing pattern 124 increases to realize low resistance and the aspect ratio of the conductive pattern 120a increases, etching defects may be caused by the silver residue and overeating angle. However, a wet etching process in which the etch failure is suppressed using the etchant composition according to the exemplary embodiments can be realized.

3 is a schematic sectional view showing a conductive pattern shape formed according to a comparative example. For example, the comparative example shows the shape of the conductive pattern 140 formed using the phosphoric acid etchant composition.

Referring to FIG. 3, when the phosphoric acid etchant composition is used, a tip 150 is formed on the side of the first and second transparent conductive oxide film patterns 142 and 146, ) Can be caused. In this case, tearing and peeling of the insulating film covering the conductive pattern 140 may occur.

Also, when the lower conductive pattern 115 is exposed while the conductive pattern 140 is formed, the lower conductive pattern 115 is partially etched and damaged by the phosphoric acid etchant composition to cause the recess 155 . In addition, the lower insulating film 110 may be damaged together with the phosphoric acid etchant composition.

However, according to the exemplary embodiments, the phosphoric acid or phosphate-free etchant composition is used to form a highly reliable wet etch process with reduced damage to the conductive pattern 120a and the lower conductive pattern 115, The process can be carried out.

4 is a schematic cross-sectional view for explaining a conductive pattern forming method according to exemplary embodiments.

Referring to FIG. 4, as the area of the substrate 100 on which the metal film 120 is formed is increased, the substrate 100 is tilted so as to be inclined at a predetermined angle in order to prevent etching efficiency and breakage of the substrate 100 ). Thereafter, the etchant composition may be sprayed onto the metal film 120 formed on the inclined substrate 100 through the etchant injection equipment 50.

In the comparative example, when the high-viscosity phosphoric acid etchant composition is used, the lower portion (the right portion in FIG. 3) of the substrate 100 may be dipped or dipped for a relatively long time by the etchant composition to damage or lose the conductive pattern.

However, the etchant compositions according to the exemplary embodiments can have low viscosity by eliminating phosphoric acid or phosphate, and can reduce etching variations due to height or position differences.

5 is a schematic cross-sectional view illustrating an image display device manufactured in accordance with some exemplary embodiments.

Referring to FIG. 5, a thin film transistor (TFT) may be formed on a substrate 200. For example, the TFT may include an active layer 210, a gate insulating film 220, and a gate electrode 225.

According to exemplary embodiments, after the active layer 210 is formed on the substrate 200, the gate insulating film 220 covering the active layer 210 may be formed.

The active layer 210 may be formed to include an oxide semiconductor such as polysilicon or, for example, indium gallium zinc oxide (IGZO). The gate insulating film 220 may be formed to include silicon oxide, silicon nitride, and / or silicon oxynitride.

A gate electrode 225 may be formed on the gate insulating layer 220 to overlap with the active layer 210. The gate electrode 225 may be formed to include a metal such as Al, Ti, Cu, W, Ta, Ag, or the like.

The interlayer insulating film 230 covering the gate electrode 225 is formed on the gate insulating film 220 and then the source electrode 233 which is in contact with the active layer 210 through the interlayer insulating film 230 and the gate insulating film 220 And the drain electrode 237 can be formed. The source electrode 233 and the drain electrode 237 may be formed to include a metal such as Al, Ti, Cu, W, Ta, or Ag.

A via insulating film 240 covering the source electrode 233 and the drain electrode 237 may be formed on the interlayer insulating film 230. The via insulating film 240 may be formed using an organic insulating material such as an acrylic type, a siloxane type resin, or the like.

A pixel electrode 245 electrically connected to the drain electrode 237 may be formed on the via insulating layer 240. The pixel electrode 245 may include a via portion that contacts the drain electrode 237 through the via insulating layer 240. The pixel electrode 245 may be formed to include a metal such as Al, Ti, Cu, W, Ta, Ag, and / or a transparent conductive oxide.

The pixel defining layer 250 may be formed on the via insulating layer 240 and the display layer 255 may be formed on the pixel defining layer 250 exposed by the pixel defining layer 250. The display layer 255 may be formed of, for example, a liquid crystal layer included in an organic light emitting layer (EML) or an LCD device included in an OLED device.

The counter electrode 260 may be formed on the pixel defining layer 250 and the display layer 255. The counter electrode 260 may be provided as a common electrode, a reflective electrode, or a cathode of an image display apparatus.

According to exemplary embodiments, the counter electrode 260 may be formed by sequentially laminating a first transparent conductive oxide film, a silver-containing film, and a second transparent conductive oxide film, and then patterning through a wet etching process using the above- .

Thus, the counter electrode 260 includes the first transparent conductive oxide film pattern 262, the silver-containing pattern 124 and the second transparent conductive oxide film pattern 262 sequentially stacked on the pixel defining layer 250 and the display layer 255. [ (266).

In some embodiments, the image display device may include a display area I and a non-display area II. The TFT, the pixel electrode 245, the display layer 255, and the counter electrode 260 described above can be formed on the display region I. A wiring 270 may be formed on the non-display area II. The wiring 270 may be electrically connected to the TFT or the counter electrode 260.

The wiring 270 also includes a first transparent conductive oxide film pattern 272, a silver-containing pattern 274 and a second transparent conductive oxide film pattern 276 which are sequentially stacked, for example, on the via insulating film 240, May be patterned using the etchant composition in accordance with the illustrative embodiments.

In one embodiment, the lines 270 may be formed together by a wet etch process that is substantially the same as the counter electrodes 260 on the display area I.

As described above, by forming the counter electrode 260 and / or the wiring 270 of the image display apparatus in a laminated structure including the first transparent conductive oxide film pattern-containing pattern-second transparent conductive oxide film pattern, While implementing resistance properties, mechanical / chemical stability and optical properties can be improved together. Further, by using the etching solution composition containing an organic oxidizing agent, defects such as silver residue, side damage, tip developing and the like can be suppressed.

6 is a schematic plan view illustrating a touch sensor formed in accordance with some exemplary embodiments.

Referring to FIG. 6, the touch sensor 300 may include a sensing electrode 310, a trace 320, and a pad 330 formed on a substrate 300.

The touch sensor 300 may include a sensing area A and a peripheral area B. [ The trace 320 and the pad 330 may be formed on the substrate 300 of the sensing area A of the sensing electrode 310 and the trace 320 and the pad 330 may be formed on the substrate 300 of the peripheral area B.

The sensing electrode 310 may include a first sensing electrode 310a and a second sensing electrode 310b arranged in a first direction and a second direction that are parallel to the upper surface of the substrate 300 and cross each other at right angles, . &Lt; / RTI &gt;

The first sensing electrode 310a extends in the first direction and a plurality of first sensing electrodes 310a may be formed along the second direction. The second sensing electrode 310b may extend in the second direction and may include a plurality of second sensing electrodes 310b along the first direction.

Each of the first and second sensing electrodes 310a and 310b may include a polygonal unit pattern, for example, and may include a connection unit for connecting neighboring unit patterns. The inside of the unit pattern may include a conductive pattern patterned in a mesh type.

A trace 320 may be branched from each of the sensing electrodes 310a and 310b and a distal end of the trace 320 may be connected to the pad 330. [ The touch sensor 300 may be connected to an external circuit such as a flexible printed circuit board (FPCB) through a pad 330.

According to exemplary embodiments, the trace 320 may be formed through a wet etch process using an etchant composition comprising the above-described organic oxidant. In some embodiments, the trace 320 may be formed in a stacked structure of a first transparent conductive oxide film pattern-containing pattern-second transparent conductive oxide film pattern.

In one embodiment, sensing electrode 310 and / or pad 330 may also be formed through a wet etch process using the etchant composition. For example, the sensing electrode 310 and / or the pad 330 may be formed together through a wet etch process that is substantially the same as the trace 320. In this case, the sensing electrode 310 and / or the pad 330 may also be formed as a laminated structure of the first transparent conductive oxide film pattern-containing pattern-second transparent conductive oxide film pattern.

As the conductive patterns of the touch sensor 300 include the above-described laminated structure of the silver-containing pattern and the transparent conductive oxide film pattern, the mechanical stability such as the electrical property such as the sensing sensitivity and the crack resistance can be improved together.

As described above, various conductive patterns having improved electrical, mechanical, and chemical properties can be formed by using the metal film etchant composition according to the exemplary embodiments, which are included in an image display device, a touch sensor, and the like.

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the spirit and scope of the appended claims.

Examples and Comparative Examples

The metal film etchant compositions according to Examples and Comparative Examples were prepared with the components and the contents (% by weight) shown in Table 1 below.

division Composition (% by weight) Organic oxidizer Etching
Enhancer Inorganic acid water
(Deionized water) Glycolic acid Malonic acid methane
Sulfonic acid Lactic acid Citric acid Example 1 50 - - - - Nitric acid: 8 - Balance Example 2 - 40 - - - Nitric acid: 9 - Balance Example 3 - - 50 - - Nitric acid: 9 - Balance Example 4 - - - 38 - Nitric acid: 7 - Balance Example 5 - - - - 65 Nitric acid: 5 - Balance Example 6 50 10 - - - Nitric acid: 3 - Balance Example 7 - 20 30 - 10 Nitric acid: 2 - Balance Example 8 10 10 10 10 10 Nitric acid: 5 - Balance Example 9 - - - 60 5 Nitric acid: 4 - Balance Example 10 10 10 10 - 10 Nitric acid: 4 - Balance Example 11 10 10 10 10 10 Sulfuric acid: 5 - Balance Example 12 50 - - - - Sulfuric acid: 9 - Balance Example 13 10 10 10 10 30 Nitric acid: 5 - Balance Comparative Example 1 75 - - - - Nitric acid: 8 - Balance Comparative Example 2 50 - 30 - - Nitric acid: 5 - Balance Comparative Example 3 - 40 - - - Nitric acid: 12 - Balance Comparative Example 4 - - 50 - - Nitric acid: 0.5 - Balance Comparative Example 5 - - - 30 - Nitric acid: 5 - Balance Comparative Example 6 - - - - 80 Nitric acid: 5 - Balance Comparative Example 7 - 40 - 40 - Nitric acid: 5 - Balance Comparative Example 8 - - - - - Nitric acid: 8 Phosphoric acid: 40 Balance Comparative Example 9 - - 30 - - Nitric acid: 5 Phosphoric acid: 30 Balance

Experimental Example

(One) Etching  Character rating

A triple film of ITO (100 Å) / Ag (1000 Å) / ITO (100 Å) was formed on a glass substrate, and a sample cut into a size of 10 cm × 10 cm was prepared using a diamond knife.

The metal film etching solution compositions of Examples and Comparative Examples were injected into a spray type etching equipment (ETCHER, K.C.Tech). When the temperature of the metal film etchant composition was set to 40 占 폚 and the temperature reached 40 占 0.1 占 폚, the metal film etchant composition was sprayed onto the sample and the etching process was performed for 85 seconds.

After the etching process was completed, the sample was rinsed with deionized water, dried using a hot air drying apparatus, and the photoresist was removed using a photoresist stripper (PR stripper).

(1-1) Side Etch / Etching  Distance Rating

The etched samples were measured for the average etch distance between the side etch of the conductive pattern formed by using an electronic scanning microscope (SU-8010, manufactured by Hitachi) and the upper and lower portions of the substrate.

The side etch (S / E) was calculated by the following equation (1) and evaluated as follows.

[Equation 1]

Side etch (S / E) = ((width of photoresist both ends) - (width of etched wiring width)) / 2

?: Excellent (0.5 占 퐉 or less)

?: Good (more than 0.5 占 퐉 and not more than 1.0 占 퐉)

X: defective (exceeding 1.0 占 퐉)

The evaluation criteria of the etching distance distribution are as follows.

?: Excellent (less than 0.1 占 퐉)

?: Good (exceeding 0.1 占 퐉 and not more than 0.5 占 퐉)

X: defective (exceeding 0.5 占 퐉)

(1-2) Ag ) Residue  And processing number ( Etching  Performance maintenance) evaluation

After completion of the etching, the occurrence of silver residue or dark spot on the substrate was observed. After the completion of the etching, the etching performance was evaluated by solubility measurement as follows.

◎: Excellent (silver solubility 1000 ppm or more)

Good: good (silver solubility 500 ppm or more, less than 1000 ppm)

X: poor (silver solubility less than 500 ppm)

(2) Evaluation of damage to substructure

A triple film structure of Mo / Al / Mo (total thickness: 1000 ANGSTROM) was formed on a glass substrate, and a sample cut into a size of 10 cm x 10 cm was prepared using a diamond knife. The etchant composition was sprayed on the sample in the same manner as in the evaluation of the etching characteristics, and then the etching of the triple-layer structure was observed using an electron scanning microscope (SU-8010, manufactured by HITACHI).

The evaluation results of the above-described experimental examples are shown together in Table 2 below.

division side
Etch Etching distance
Distribution Ag residue Number of processing Substructure
damaged Example 1 ◎ ◎ 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 Example 8 ◎ ◎ none ◎ none Example 9 ○ ◎ none ◎ none Example 10 ○ ◎ none ◎ none Example 11 ○ ◎ none ◎ none Example 12 ○ ◎ none ◎ none Example 13 ○ ◎ none ◎ none Comparative Example 1 X X none ◎ none Comparative Example 2 X X none ◎ none Comparative Example 3 X ◎ none X none Comparative Example 4 ○ ◎ Occur ○ none Comparative Example 5 ○ ◎ Occur X none Comparative Example 6 X X none ◎ none Comparative Example 7 X X none ◎ none Comparative Example 8 X X Occur ◎ Occur Comparative Example 9 X X Occur ◎ Occur

Referring to Table 2, in the case of the etching composition containing 35 to 70% by weight of the organic oxidizing agent and 1 to 10% by weight of the etching promoter, excellent etching characteristics were exhibited as compared with the comparative examples, Lt; / RTI &gt;

For example, in the case of Comparative Examples 1, 2, 6 and 7, in which the organic oxidizing agent is included in an excess amount, and in Comparative Example 3, in which the content of the etching enhancer is somewhat excessive, side etch and / or etching distance characteristics are deteriorated. On the other hand, in the case of Comparative Examples 4 and 5 in which the content of the organic oxidizing agent or the etching promoter was decreased, residues were generated and the etching performance holding power was somewhat lowered.

In the case of Comparative Examples 8 and 9 containing phosphoric acid, the etching property was rapidly deteriorated, and damage of the lower structure was observed.

100, 200: substrate 110: lower insulating film
115: lower conductive pattern 120: metal film
120a, 140: conductive pattern 121: first transparent conductive oxide film
122, 142, 262, 272: a first transparent conductive oxide film pattern
123: silver containing film 124, 144, 264, 274: silver containing pattern
125: second transparent conductive oxide film
126, 146, 266, and 276: a second transparent conductive oxide film pattern
210: active layer 210: gate electrode
233: source electrode 237: drain electrode
245: pixel electrode 260: opposing electrode
270: Wiring 300: Touch sensor
310: sensing electrode 320: trace
330: Pad

Claims (16)

Of the total weight of the composition,
35 to 70% by weight of an organic oxidant;
1 to 10% by weight of an etching enhancer comprising an inorganic acid; And
A metal film etchant composition comprising an excess of water.
The method according to claim 1, wherein the organic oxidant is selected from the group consisting of methanesulfonic acid, glycolic acid, formic acid, malonic acid, citric acid, lactic acid, malic acid, gluconic acid, sulfamic acid, para toluenesulfonic acid, iminodiacetic acid, oxalic acid, tartaric acid and ascorbic acid And at least one selected.
The metal film etch composition of claim 1, wherein the etch enhancer comprises at least one of nitric acid or sulfuric acid.
The metal film etchant composition of claim 1, wherein the metal film comprises a silver-containing film.
The metal film etch composition according to claim 4, wherein the metal film further comprises a transparent conductive oxide film.
The metal film etch composition according to claim 5, wherein the transparent conductive oxide film comprises a first transparent conductive oxide film and a second transparent conductive oxide film formed with the silver-containing film therebetween.
[6] The method according to claim 5, wherein the transparent conductive oxide film is formed from a group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium zinc oxide (GZO) and indium gallium zinc oxide (IGZO) And at least one selected.
The metal film etchant composition according to claim 1, which does not contain a phosphoric acid or phosphoric acid-based compound.
The composition according to claim 1,
40 to 60 wt% of the organic oxidant; 5 to 10% by weight of the etch enhancer; And an excess of water.
Forming a metal film on the substrate; And
And etching the metal film using the metal film etchant composition of any one of claims 1 to 9.
11. The method of claim 10, wherein forming the metal film comprises forming a silver containing film.
12. The method of claim 11, wherein forming the metal film further comprises forming a transparent conductive oxide film.
11. The method of claim 10, further comprising tilting the substrate on which the metal film is formed.
The method of claim 10,
Forming a thin film transistor on the substrate;
Forming a pixel electrode electrically connected to the thin film transistor; And
Forming a display layer on the pixel electrode,
Wherein the metal film is formed on the display layer.
15. The conductive pattern forming method according to claim 14, wherein the conductive pattern is provided as a common electrode, a reflective electrode, or a wiring of an image display apparatus.
15. The method of claim 14, wherein the conductive pattern is provided as a trace or sensing electrode of a touch sensor.

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