KR20190011984A - Etchant composition for etching metal layer and method of forming conductive pattern using the same - Google Patents

Abstract

Various embodiments of the present invention provide a metallic film etchant composition, comprising in the total weight of the composition: 50 to 65 wt% of phosphoric acid, 6 to 9 wt% of nitric acid, 0.1 to 3 wt% of phosphate, 0.1 to 3 wt% of acetate, and extra water. By using the metallic film etchant composition, a conductive pattern can be formed with less etching deviation and etching failure.

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 .

The etchant composition generally comprises a large amount of acid components. The etching characteristics may vary depending on the kind of the acid components, and defects such as overeating angle, gourmet angle, etch residue may be caused.

In addition, when the acid component of the acid component contains a large amount of an acid solution having a high steam pressure or a high volatility, if the etching process is carried out for a long time, the composition ratio may vary and uniform etching characteristics may not be obtained.

In recent years, when the stability of the etchant composition with respect to changes over time is not ensured as the display substrate or the display screen becomes larger, it is difficult to form a conductive pattern having a desired critical dimension.

For example, Korean Patent No. 10-0579421 discloses a silver etchant composition, but it may be vulnerable to the above-described aging change as it contains a large amount of volatile components.

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 high resolution.

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

One aspect of the present invention is to provide a method of manufacturing a display substrate using the metal film etchant composition.

1. 50 to 65% by weight phosphoric acid, based on the total weight of the composition; 6 to 9% by weight of nitric acid; 0.1 to 3% by weight of phosphate; 0.1 to 3% by weight of acetic acid; And an excess of water.

2. The method of claim 1, wherein the phosphate is selected from the group consisting of sodium monophosphate, sodium diphosphate, sodium dibasic, potassium monophosphate, dibasic potassium phosphate, ammonium monophosphate, ammonium dibasic and ammonium triphosphate And at least one selected from the group consisting of the metals.

3. The metal film etchant composition of claim 1, wherein the acetate salt comprises at least one selected from the group consisting of ammonium acetate, sodium acetate, and potassium acetate.

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

5. The metal film etchant composition of claim 1, wherein the acetic acid is absent.

6. The metal film etchant composition of claim 5, wherein the metal film etchant composition comprises phosphoric acid, nitric acid, phosphoric acid salt, acetic acid salt, and excess water.

7. A method for manufacturing a semiconductor device, comprising: forming a metal film on a substrate; And

And etching the metal film using the metal film etchant composition of any one of [1] to [6] above.

8. The method of forming a conductive pattern according to 7 above, wherein the step of forming the metal film includes a step of laminating a silver-containing film and at least one transparent conductive oxide film.

9. The transparent conductive oxide film of claim 8, 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) ≪ / RTI > wherein at least one selected from the group < RTI ID = 0.0 >

10. The method of forming a conductive pattern according to 7 above, further comprising a step of tilting the substrate on which the metal film is formed.

11. In above 7,

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.

12. The method for forming a conductive pattern according to 11 above, wherein the conductive pattern is provided as a common electrode, a reflective electrode or a wiring of an image display apparatus.

13. The method of forming a conductive pattern according to 7 above, wherein the conductive pattern is provided as a trace or sensing electrode of a touch sensor.

The metal film etchant composition according to the embodiments of the present invention includes phosphoric acid, nitric acid, phosphate, acetate, and water, and substantially no acetic acid can be excluded. Therefore, since acetic acid having high volatility is removed, uniform etching characteristics can be secured even in a long-term large-scale etching process.

According to exemplary embodiments, as the phosphate and the acetate salt are used together, the etching fine suppression effect of the transparent conductive oxide and the silver-containing film can be realized together to improve the etching profile.

Using the etchant composition, for example, an electrode or wiring such as a reflective electrode of a 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.

1 to 3 are sectional views for explaining a conductive pattern forming method according to exemplary embodiments.
4 is a cross-sectional view illustrating a method of manufacturing a display substrate according to exemplary embodiments.
5 is a schematic plan view illustrating a touch sensor made in accordance with exemplary embodiments.

According to embodiments of the present invention, a metal film etchant composition (hereinafter abbreviated as "etchant composition") comprising phosphoric acid, nitric acid, phosphate, acetate and water is provided. A conductive pattern forming method and a display substrate manufacturing method using the metal film etchant composition are also 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 film 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 &

In the etchant composition according to the embodiments of the present invention, phosphoric acid (H ₃ PO ₄ ) may function as a main oxidizing agent for the silver containing film and / or the transparent conductive oxide film.

According to exemplary embodiments, the phosphoric acid may be included in an amount of about 50 to 65 weight percent of the total weight of the composition. If the content of phosphoric acid is less than about 50% by weight, the etching rate for the silver-containing film may be excessively inhibited, resulting in a substantial unfavorable angle. If the content of phosphoric acid exceeds about 65 wt%, the etching rate of the silver-containing film to the transparent conductive oxide film may excessively increase to cause a tip phenomenon. In addition, the viscosity of the composition may be excessively increased, and the etching variations may be intensified in the upper and lower conductive patterns.

The nitric acid (HNO ₃ ) may be included as the auxiliary oxidizing agent for the silver-containing film and / or the transparent conductive oxide film.

According to exemplary embodiments, the nitric acid may be included in an amount of about 6 to 9 weight percent of the total weight of the composition. When the content of nitric acid is less than about 6% by weight, the etching rate for the silver-containing film and the transparent conductive oxide film is excessively inhibited to cause, for example, silver residue, ITO residue and the like, have. If the content of nitric acid exceeds about 9 wt%, the etching rate of the transparent conductive oxide film to the silver-containing film may excessively increase to cause protrusion of the silver pattern.

As described above, by controlling the contents of phosphoric acid and nitric acid, a balance of etching rates of the silver-containing film and the transparent conductive oxide film can be maintained and a conductive pattern having a desired etching profile can be obtained.

According to exemplary embodiments, the etchant composition may comprise a phosphate and a nitrate. When the phosphate and the acetate are used together, the silver-containing film and the transparent conductive oxide film can be simultaneously reduced in etching rate and passivated. In addition, the critical dimension bias (CD Bias) characteristic of the conductive pattern can be improved.

For example, the nitrate salt can prevent an excessive increase in the etching rate of the transparent conductive oxide film, thereby preventing the top surface of the silver-containing film from being exposed. In addition, the phosphate may passivate the sidewall of the silver-containing film to prevent the over-heating angle from progressing through the sidewall of the silver-containing film.

The phosphate may be, for example, sodium phosphate (NaH ₂ PO ₄ ), dibasic sodium phosphate (Na ₂ HPO ₄ ), sodium phosphate dibasic (Na ₃ PO ₄ ), potassium monophosphate (KH ₂ PO ₄ ) , dipotassium hydrogen phosphate (K ₂ HPO _4), first ammonium phosphate ((NH ₄₎ H ₂ PO _4), the second ammonium phosphate ((NH _{4) 2} HPO _4), a third ammonium phosphate ((NH _{4) 3} PO ₄ ), and the like. These may be used alone or in combination of two or more.

In some embodiments, the phosphate may be included in an amount of about 0.1 to 3 weight percent of the total weight of the composition. If the content of the phosphate is less than about 0.1% by weight, etching uniformity may be deteriorated, resulting in silver residues and the like. If the content of the phosphate exceeds about 3 wt%, the action of phosphoric acid and / or nitric acid may be impaired and the etching rate may be excessively inhibited.

The acetic acid salt may include, for example, ammonium acetate, sodium acetate, potassium acetate, and the like. These may be used alone or in combination of two or more.

In some embodiments, the acetic acid salt may be included in an amount of about 0.1 to 3% by weight of the total composition. If the amount of the acetate is less than about 0.1% by weight, etching uniformity may be inhibited, and silver residues may be generated. If the amount of the acetate is more than about 3 wt%, the action of phosphoric acid and / or nitric acid may be impaired and the etching rate may be excessively inhibited.

The etchant composition may include excess or residual water except for the above-mentioned components, for example, deionized water. 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 remaining amount " as used in the present application means a variable amount including the amounts of the above-mentioned components and the above additives, 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 components described above. For example, the additive may include anti-corrosion, anti-adhesion of etching by-products, formulation for adjusting the taper angle of the etching pattern, and the like widely used in the art.

In some embodiments, the etchant composition may be substantially composed of the aforementioned phosphoric acid, nitric acid, phosphates, nitrates, and water.

According to exemplary embodiments, the etchant composition may not include acetic acid. In the case of acetic acid, since it has a high vapor pressure or volatility, if the etching process is continued for a long time, the stability with time of the acetic acid-containing composition may deteriorate. For example, it is difficult for the acetic acid to evaporate and remove during the etching process to maintain a uniform etching rate. In addition, when the etching process is performed on a large area substrate, the composition content may vary for each region, and it may be difficult to form a conductive pattern having a uniform size distribution.

However, as described above, the etchant composition according to the embodiments of the present invention can exclude acetic acid. For example, water and / or acetate may be substituted for the acetic acid-free portion of the content to reduce volatility and viscosity of the composition as a whole.

Therefore, the stability of the etchant composition over time can be improved, and the flowability can be improved, thereby effectively suppressing local pattern loss and pattern failure.

According to some embodiments, the etchant composition may not include hydrochloric acid and sulfuric acid. Thus, an environmental pollution problem and an etching process with reduced silver precipitation problems can be realized.

<Conductive Pattern Forming Method>

1 to 3 are sectional views for explaining a conductive pattern forming method according to exemplary embodiments.

1 to 3 are sectional views for explaining a conductive pattern 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.

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.

Referring to FIG. 3, when the area of the substrate 100 is enlarged, one end of the substrate 100 is tilted upward to be inclined for ease of the wet etching process, and then the etching solution is injected through the etchant injection device 50 Etching of the metal film 120 formed on the substrate 100 can be performed by spraying the etchant composition.

In this case, since the etchant composition flows along the oblique direction of the substrate 100, a difference in etch rate may occur between the upper portion and the lower portion of the substrate 100. For example, when the etchant composition is excessively concentrated or buried under the substrate 100, the metal film 120 formed on the lower portion of the substrate 100 may be excessively etched to cause a problem of the lower wiring loss. When the stability with time is deteriorated due to a change in the content of the composition, the above-described etching variations can be further intensified.

However, as described above, since the etchant composition according to the exemplary embodiments excels in acetic acid and has an increased stability over time, and has a relatively low viscosity composition, A desired uniform conductive pattern can be formed. In addition, the intricate or superposed angle of any of the silver-containing film and the transparent conductive oxide film can be blocked by the interaction of the phosphate and the acetate.

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.

4 is a cross-sectional view illustrating a method of manufacturing a display substrate according to exemplary embodiments. For example, Fig. 4 shows a display substrate including a wiring and an electrode structure formed by the conductive pattern forming method described above.

Referring to FIG. 4, 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, as the above-described etching liquid composition is used, an electrode or a wiring having no upper and lower etching deviation in a large-area display can be formed.

In some embodiments, patterning of the gate electrode 225, the source electrode 233, the drain electrode 237, and the pixel electrode 245 may be performed utilizing the etching solution composition or the conductive pattern forming method described above.

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

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

The touch sensor 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 which are parallel to the upper surface of the substrate 300 and intersect perpendicularly to each other, . &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 traces 320 may be formed through a wet etch process using the etchant composition described above. 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 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.

Phosphoric acid nitric acid Acetic acid phosphate
(Sodium phosphate monobasic) acetate
(Ammonium acetate) water Example 1 50.0 6.0 - 0.1 0.1 Balance Example 2 65.0 6.0 - 0.1 0.1 Balance Example 3 50.0 9.0 - 0.1 0.1 Balance Example 4 65.0 9.0 - 0.1 0.1 Balance Example 5 50.0 6.0 - 3.0 3.0 Balance Example 6 50.0 9.0 - 3.0 3.0 Balance Example 7 65.0 6.0 - 3.0 3.0 Balance Example 8 65.0 9.0 - 3.0 3.0 Balance Comparative Example 1 45.0 9.0 0.0 3.0 3.0 Balance Comparative Example 2 67.0 9.0 0.0 3.0 3.0 Balance Comparative Example 3 50.0 5.0 0.0 3.0 3.0 Balance Comparative Example 4 50.0 10.0 0.0 3.0 3.0 Balance Comparative Example 5 50.0 6.0 0.0 0.0 0.0 Balance Comparative Example 6 50.0 6.0 0.0 4.0 4.0 Balance Comparative Example 7 50.0 6.0 5.0 3.0 3.0 Balance Comparative Example 8 50.0 6.0 10.0 3.0 3.0 Balance Comparative Example 9 50.0 6.0 15.0 3.0 3.0 Balance Comparative Example 10 50 6.0 0.0 3.0 - Balance Comparative Example 11 50 6.0 0.0 - 3.0 Balance

Experimental Example

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) Wiring loss evaluation / viscosity measurement

The etched samples were evaluated for side-etched wiring patterns by using a scanning electron microscope (SU-8010, manufactured by Hitachi). Specifically, in the first etching step and the etching step after 24 hours from the preparation of the composition, the degree of wiring loss and the composition viscosity were evaluated (glass substrate tilting angle: 10 ^° ) at the top and bottom of the glass substrate, respectively.

The wiring loss (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)

(2) Threshold Count  Measurement of bias (CD bias)

After completion of the etching, the substrate was washed with deionized water and then dried using a hot air drying apparatus. After cleaning and drying, the substrate was cut and its cross-section was measured using an electron microscope (SEM; model: SU-8010, manufactured by Hitachi). The threshold value bias evaluation was performed by measuring the upper width of the wiring in contact with the photoresist pattern after completion of the etching. The evaluation criteria are as follows.

?: Width of the wiring in contact with the photoresist exceeds 31 占 퐉 to 34 占 퐉

?: Width of the wiring in contact with the photoresist exceeds 23 占 퐉 to 31 占 퐉

DELTA: Width of the wiring in contact with the photoresist is more than 9 mu m and not more than 23 mu m

X: Width of the wiring which is not etched or in contact with the photoresist is 9 占 퐉 or less

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

division Initial use After 24 hours CD-Bias Wiring loss Viscosity
(cp) Wiring loss Viscosity
(cp) Substrate top Substrate bottom Substrate top Substrate bottom Example 1 ◎ ◎ 4.12 ◎ ◎ 5.92 ◎ Example 2 ◎ ◎ 5.02 ◎ ◎ 6.78 ◎ Example 3 ◎ ◎ 4.21 ◎ ◎ 5.99 ◎ Example 4 ◎ ◎ 5.28 ◎ ◎ 6.89 ◎ Example 5 ◎ ◎ 4.19 ◎ ◎ 6.02 ◎ Example 6 ◎ ◎ 4.29 ◎ ◎ 6.10 ◎ Example 7 ◎ ◎ 5.11 ◎ ◎ 6.90 ◎ Example 8 ◎ ◎ 5.24 ◎ ◎ 6.92 ◎ Comparative Example 1 Gourmet angle Gourmet angle 3.68 Gourmet angle Gourmet angle 5.30 Gourmet angle Comparative Example 2 ◎ ◎ 5.30 X X 7.60 △ Comparative Example 3 Gourmet angle Gourmet angle 4.02 Gourmet angle Gourmet angle 5.88 Gourmet angle Comparative Example 4 ◎ ◎ 4.23 ○ X 6.01 ○ Comparative Example 5 ○ ○ 4.11 ○ X 5.82 X Comparative Example 6 Gourmet angle Gourmet angle 4.25 Gourmet angle Gourmet angle 5.99 Gourmet angle Comparative Example 7 ○ ○ 5.52 ○ X 7.84 X Comparative Example 8 ○ ○ 6.12 ○ X 8.34 X Comparative Example 9 ○ ○ 6.40 ○ X 8.95 X Comparative Example 10 ○ ○ 4.08 ○ ○ 5.01 △ Comparative Example 11 ○ ○ 4.05 ○ ○ 5.03 △

Referring to Table 2, the etchant composition according to the Examples maintained stable etching performance even after 24 hours, and pattern loss and etching deviation did not occur.

However, in the case of the comparative examples exceeding the content range according to the embodiments of the present invention or including acetic acid, the angle of incongruity occurred or the wiring loss after 24 hours was intensified.

On the other hand, in the case of Comparative Examples 10 and 11 in which either phosphate or acetate was absent, the CD-bias characteristic deteriorated and the aging stability was somewhat reduced as compared with the Examples.

100, 200: substrate 110: lower insulating film
115: lower conductive pattern 120: metal film
120a: conductive pattern 121: first transparent conductive oxide film
122, 262, and 272: a first transparent conductive oxide film pattern
123: Silver-containing film 124, 264, 274: silver-containing pattern
125: second transparent conductive oxide film
126, 266, 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: substrate
310: sensing electrode 320: trace
330: Pad

Claims (13)

Of the total weight of the composition,
50 to 65 wt% phosphoric acid;
6 to 9% by weight of nitric acid;
0.1 to 3% by weight of phosphate;
0.1 to 3% by weight of acetic acid; And
Wherein the metal film etchant composition comprises excess water.
The method of claim 1, wherein the phosphate is selected from the group consisting of sodium phosphate, sodium phosphate dibasic, sodium phosphate dibasic, potassium phosphate dibasic, potassium phosphate dibasic, ammonium phosphate dibasic, ammonium dibasic and ammonium phosphate &Lt; / RTI &gt;
The metal film etchant composition of claim 1, wherein the nitrate salt comprises at least one selected from the group consisting of ammonium acetate, sodium acetate, and potassium acetate.
The metal film etchant composition of claim 1, wherein the metal film comprises a silver-containing film and a transparent conductive oxide film.
The metal film etchant composition of claim 1, wherein the acetic acid is absent.
The metal film etch composition according to claim 5, comprising phosphate, nitric acid, the phosphate, the acetate, and the balance 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 6.
8. The method according to claim 7, wherein forming the metal film includes laminating a silver-containing film and at least one transparent conductive oxide film.
The method of claim 8, wherein the transparent conductive oxide film is formed of a material selected from the 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) A method for forming a conductive pattern, comprising at least one selected
8. The method of claim 7, further comprising tilting the substrate on which the metal film is formed.
The method of claim 7,
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.
The conductive pattern forming method according to claim 11, wherein the conductive pattern is provided as a common electrode, a reflective electrode, or a wiring of an image display apparatus.
8. The method of claim 7, wherein the conductive pattern is provided as a trace or sensing electrode of a touch sensor.

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