KR20170006242A - Method for manufacturing transparent electrode - Google Patents

Method for manufacturing transparent electrode Download PDF

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KR20170006242A
KR20170006242A KR1020150174338A KR20150174338A KR20170006242A KR 20170006242 A KR20170006242 A KR 20170006242A KR 1020150174338 A KR1020150174338 A KR 1020150174338A KR 20150174338 A KR20150174338 A KR 20150174338A KR 20170006242 A KR20170006242 A KR 20170006242A
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layer
metal
oxide
metal pattern
oxide layer
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KR1020150174338A
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Korean (ko)
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KR101789295B1 (en
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정우석
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한국전자통신연구원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a transparent electrode, comprising: sequentially laminating a first oxide layer, a metal layer, and a second oxide layer on a transparent substrate to form a multilayer transparent conductive film; forming a mask pattern on the second oxide layer Forming a trench for exposing an upper surface of the metal layer in the second oxide layer by performing an etching process using the mask pattern as an etch mask and forming a metal pattern in the trench, And a manufacturing method thereof.

Figure P1020150174338

Description

METHOD FOR MANUFACTURING TRANSPARENT ELECTRODE [0002]

The present invention relates to a method of manufacturing a transparent electrode, and more particularly, to a method of manufacturing a transparent electrode having a metal pattern of a mesh structure.

BACKGROUND ART [0002] Recently, transparent electrodes are generally used as electrodes of electronic devices such as solar cells and organic EL (electroluminescence) devices. Particularly, in fields such as next generation touch sensors and transparent heaters, large area transparent electrodes having a high transmittance of about 90% and a low resistance of 10 Ω / □ or less are required. Currently, transparent electrodes used in the industry are transparent conductive oxides (TCO), hybrid transparent electrodes of an oxide / metal / oxide (OMO) structure, or metal electrodes of a mesh structure. The metal electrode of the mesh structure is formed of a bulk metal in a planar network form.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a transparent electrode including a metal mesh of a mesh structure.

Another object of the present invention is to provide a method of manufacturing a transparent electrode having a low resistance and high transparency.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to another aspect of the present invention, there is provided a method of fabricating a transparent electrode, including: forming a transparent conductive film by sequentially laminating a first oxide layer, a metal layer, and a second oxide layer on a transparent substrate; Forming a mask pattern on the second oxide layer and performing an etch process using the mask pattern as an etch mask to form a trench exposing an upper surface of the metal layer in the second oxide layer, To form a metal pattern

According to one embodiment, the metal pattern may have a mesh structure in a plan view.

According to one embodiment, the metal pattern includes first metal patterns extending in one direction in a planar manner, and second metal patterns extending in a direction perpendicular to the first direction to form a plurality of rows And the like.

According to one embodiment, the metal pattern may have a honeycomb shape in a plan view.

According to one embodiment, forming the metal pattern may include performing a plating process using an upper surface of the exposed metal layer as a seed.

According to one embodiment, the plating process may use at least one selected from the group consisting of copper (Gu), nickel (Ni), silver (Ag), and alloys thereof as a source material.

According to an embodiment, the upper surface of the metal pattern may be formed to be higher than the upper surface of the second oxide layer and lower than the upper surface of the mask pattern.

According to one embodiment, the mask pattern has a height of 1 to 10 micrometers from one side of the second oxide layer, and the metal pattern has a height of 0.1 to 10 micrometers from one side of the second oxide layer Lt; / RTI >

According to one embodiment, the metal pattern may have a width of 1 to 20 micrometers.

According to one embodiment, the metal layer is made of a material selected from the group consisting of Ag, Al, Mo, Au, Pd, Ti, Cu, Or the like.

According to one embodiment, each of the first oxide layer and the second oxide layer is zinc oxide (ZnO), tin oxide (SnO2), silicon oxide (SiO 2), titanium oxide (TiO 2), silicon nitride (SiN x), ZITO (ZnO + In 2 O 3 + SnO 2), ZTO (ZnO + SnO 2), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ITO (In 2 O 3 + SnO 2) , IZO (In 2 O 3 + ZnO), and a compound thereof.

According to one embodiment, the multilayer transparent conductive film further comprises an adhesive layer, wherein the adhesive layer may be formed on at least one of the first oxide layer and the metal layer, and / or between the metal layer and the second oxide layer have.

According to one embodiment, the adhesive layer is an aluminum (Al), titanium (Ti), chromium (Cr), aluminum nitride (AlN), titanium nitride (TiN), aluminum oxide (Al 2 O 3), titanium oxide (TiO 2 ), Chromium oxide (Cr 2 O 3 ), and silicon oxide (SiO 2 , Si 3 O 4 ).

According to an embodiment, after forming the metal pattern, the method may further include forming an oxidation-preventive film on the metal pattern.

According to one embodiment, the oxidation preventing layer may include nickel (Ni) or silver (Ag).

According to an embodiment, after removing the mask pattern, the method may further include forming a protective layer to cover the second oxide layer and the metal pattern.

According to one embodiment, the protective layer may comprise silicon oxide (SiO2).

In the method of manufacturing a transparent electrode according to embodiments of the present invention, the second oxide layer can be patterned with a very fine line width of several nanometers by the nature of a photolithography process, To form a metal pattern. Therefore, the method of manufacturing a transparent electrode according to embodiments of the present invention can form a metal pattern of a mesh structure having a minute line width of several nanometers. In addition, since a simple patterning process and a plating process are used, it is easy to manufacture a large-area transparent electrode.

The transparent electrode manufactured through embodiments of the present invention has a metal pattern of a mesh structure on the multilayer transparent conductive film. Therefore, the transparent electrode can secure the low resistance property by the metal pattern while maintaining the high transmittance of the multilayer transparent conductive film, and improve the resistance uniformity of the metal pattern. In addition, a metal pattern having a fine line width exhibits excellent transmittance and can reduce optical moire phenomenon and star burst.

1 is a perspective view illustrating an example of a transparent electrode manufactured according to embodiments of the present invention.
2 is a plan view of Fig.
3 is a cross-sectional view taken along line I-I 'of Fig.
4 is a plan view for explaining another example of the metal pattern according to the embodiments of the present invention.
5 is a flowchart illustrating an example of a method of manufacturing a transparent electrode according to embodiments of the present invention.
FIGS. 6 to 10 are views for explaining an example of a method of manufacturing a transparent electrode according to embodiments of the present invention, and are cross-sectional views corresponding to I-I 'of FIG.
11 is a table showing simulation results of transparency and sheet resistance of a transparent electrode according to embodiments of the present invention.
12 is a cross-sectional view for explaining a modification of the transparent electrode according to the embodiments of the present invention.
13 is a cross-sectional view for explaining another modification of the transparent electrode according to the embodiments of the present invention.
14 is a cross-sectional view showing an example of a transparent heater to which a transparent electrode according to embodiments of the present invention is applied.
15 is an exploded perspective view showing an example of a bonded glass for a vehicle to which a transparent electrode according to embodiments of the present invention is applied.

In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It will be apparent to those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof. Those of ordinary skill in the art will understand that the concepts of the present invention may be practiced in any suitable environment. Like reference numerals refer to like elements throughout the specification.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms 'comprises' and / or 'comprising' mean that the stated element, step, operation and / or element does not imply the presence of one or more other elements, steps, operations and / Or additions.

In the present specification, when it is mentioned that a surface (or layer) is on another surface (or layer) or substrate, it may be directly formed on the other surface (or layer) or substrate, or a third surface Or layer) may be interposed.

 Although the terms first, second, third, etc. have been used in various embodiments herein to describe various regions, faces (or layers), etc., it is to be understood that these regions, Can not be done. These terms are only used to distinguish certain regions or faces (or layers) from other regions or faces (or layers). Thus, the face referred to as the first face in either embodiment may be referred to as the second face in other embodiments. Each embodiment described and exemplified herein also includes its complementary embodiments. Like numbers refer to like elements throughout the specification.

In addition, the embodiments described herein will be described with reference to cross-sectional views and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of the films and regions are exaggerated for an effective description of the technical content. Thus, the shape of the illustrations may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include changes in the shapes that are generated according to the manufacturing process. For example, the etched area shown at right angles may be rounded or may have a shape with a certain curvature. Thus, the regions illustrated in the figures have schematic attributes, and the shapes of the regions illustrated in the figures are intended to illustrate specific types of regions of the elements and are not intended to limit the scope of the invention.

The terms used in the embodiments of the present invention may be construed as commonly known to those skilled in the art unless otherwise defined.

Hereinafter, the present invention will be described in detail with reference to the preferred embodiments of the present invention with reference to the accompanying drawings.

1 is a perspective view illustrating an example of a transparent electrode manufactured according to embodiments of the present invention. 2 is a plan view of Fig. 3 is a cross-sectional view taken along line I-I 'of Fig. 4 is a plan view for explaining another example of the metal pattern according to the embodiments of the present invention. In Fig. 2, the protective layer 40 is omitted.

1 to 3, the multilayer transparent conductive film 20 may be disposed on the transparent substrate 10. [ The multilayer transparent conductive film 20 may be a hybrid electrode of an oxide / metal / oxide (OMO) structure.

According to one embodiment, the multilayer transparent conductive film 20 may comprise a sequentially sequentially stacked first oxide layer 21, a metal layer 22, and a second oxide layer 23. That is, the multilayer transparent conductive film 20 may include a first oxide layer 21 and a second oxide layer 23 facing each other with the metal layer 22 and the metal layer 22 interposed therebetween. Each of the first oxide layer 21 and the second oxide layer 23 may be formed of a material such as zinc oxide (ZnO), tin oxide (SnO 2 ), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ) (SiN x), ZITO (ZnO + In 2 O 3 + SnO 2), ZTO (ZnO + SnO 2), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ITO (In 2 O 3 + SnO 2 ), IZO (In 2 O 3 + ZnO), or a compound thereof. The first oxide layer 21 and the second oxide layer 23 may include the same material, but the embodiments of the present invention are not limited thereto. The metal layer 22 may be formed of, for example, a silver alloy containing aluminum (Al), molybdenum (Mo), gold (Au), palladium (Pd), titanium (Ti) Ag). The first oxide layer 21 and the second oxide layer 23 may have a greater thickness than the metal layer 22. In one example, each of the first oxide layer 21 and the second oxide layer 23 may have a thickness of 30 to 60 nanometers, and the metal layer 22 may have a thickness of 5 to 15 nanometers. If the thickness of the metal layer 22 is larger than the above range, the transmittance of the transparent electrode may be lowered. In addition, the first oxide layer 21 and the second oxide layer 23 may have the same thickness, but the embodiments of the present invention are not limited thereto.

According to the concept of the present invention, the second oxide layer 23 may have an opening OP that exposes the upper surface of the metal layer 22. From a plan viewpoint, the openings OP can have a mesh structure. In one example, the opening OP may have a grid shape in a plan view. In detail, the opening OP may include first openings OP1 extending in the X-direction and forming a plurality of rows and second openings OP2 extending in the Y-direction to form a plurality of rows .

The metal pattern 30 may be disposed in the opening OP. Accordingly, the metal pattern 30 can have a substantially planar structure substantially the same as the opening OP. That is, the metal pattern 30 may have a mesh structure in a plan view. For example, the metal pattern 30 may have a grid shape in a plan view. In detail, the metal pattern 30 includes first metal patterns 31 extending in the X-direction and forming a plurality of rows, second metal patterns 31 extending in the Y-direction orthogonal to the X- Patterns 32. < / RTI > The first metal patterns 31 may have a first width w1 and may be spaced apart from each other by a first distance d1. The first width w1 may correspond to the width of the first openings OP1 and the first distance d1 may correspond to the distance between the first openings OP1 adjacent to each other. Likewise, the second metal patterns 32 may have a second width w2 and may be spaced apart from each other by a second distance d2. The second width w2 may correspond to the width of the second openings OP2 and the second distance d2 may correspond to the distance between the second openings OP2 adjacent to each other. In one example, each of the first and second widths w1, w2 may be between 1 and 20 micrometers. And, each of the first and second distances d1 and d2 may be 1 to 1000 micrometers. When the first and second widths w1 and w2 are larger than the above ranges and the first and second distances d1 and d2 are smaller than the above ranges, the transmittance of the transparent electrode is lowered, and an optical moire phenomenon And a star burst may occur. According to one embodiment, the first and second widths w1 and w2 may be equal to each other, and the first and second distances d1 and d2 may be equal to each other. However, the embodiments of the present invention are not limited thereto.

The metal pattern 30 may fill the opening OP and protrude above the upper surface of the second oxide layer 23. [ For example, the metal pattern 30 may protrude from the upper surface of the second oxide layer 23 by a second height h2. As an example, the second height h2 may be 0.1 to 10 micrometers. The metal pattern 30 may comprise a highly conductive metal. For example, the metal pattern 30 may include copper (Cu), nickel (Ni), silver (Ag), or an alloy thereof.

Meanwhile, according to another embodiment, the metal pattern 30 may be implemented in various types of network structures. For example, as shown in FIG. 4, the metal pattern 30 may have a honeycomb-type mesh structure. Correspondingly, the opening OP of the second oxide layer 23 may also have the form of a honeycomb. At this time, the metal pattern 30 may have a third width w3. As an example, the third width w3 may be between 1 and 20 micrometers. The parallel metal lines of the metal pattern 30 may be spaced from each other by a third distance d3. As an example, the third distance d3 may be between 1 and 1000 micrometers.

A protective layer 40 may be disposed on the metal pattern 30. [ The protective layer 40 may cover the second oxide layer 23 and the metal pattern 30. The top surface of the protective layer 40 may have a height of 1 to 11 micrometers from the top surface of the second oxide layer 23. [ The protective layer 40 may comprise silicon oxide (SiO2). The protective layer 40 may be provided for physical protection of the metal pattern 30. According to another embodiment, the transparent electrode may not include the protective layer 40 if necessary.

Hereinafter, a method of manufacturing a transparent electrode according to embodiments of the present invention will be described with reference to FIGS. 5 to 10. FIG.

5 is a flowchart illustrating an example of a method of manufacturing a transparent electrode according to embodiments of the present invention. FIGS. 6 to 10 are views for explaining an example of a method of manufacturing a transparent electrode according to embodiments of the present invention, and are cross-sectional views corresponding to I-I 'of FIG.

Referring to FIGS. 5 and 6, the multilayer transparent conductive film 20 can be formed on the transparent substrate 10 (S10). The multilayer transparent conductive film 20 may be a hybrid electrode of an oxide / metal / oxide (OMO) structure. More specifically, the multilayer transparent conductive film 20 may be formed by sequentially laminating a first oxide layer 21, a metal layer 22, and a second oxide layer 23 on a transparent substrate 10. For example, each of the first oxide layer 21, the metal layer 22 and the second oxide layer 23 may be formed using a physical vapor deposition (PVD) method, a chemical vapor deposition (CVD) method, or a sputtering method .

5 and 7, a mask pattern M may be formed on the second oxide layer 23 (S20). The mask pattern M may be, for example, a photo resist pattern. For example, the mask pattern M may be formed by applying a photoresist on the second oxide layer 23, exposing the photoresist, and developing the exposed photoresist. At this time, the mask pattern M may be formed to have a first height h1 from the upper surface of the second oxide layer 23. The first height h1 may be between 1 and 10 micrometers. The mask pattern M may expose a part of the upper surface of the second oxide layer 23.

5 and 8, an opening OP can be formed in the multilayer transparent conductive film 20 (S30). The opening OP may be formed by etching the second oxide layer 23 using the mask pattern M as a mask. At this time, the opening OP may expose the upper surface of the metal layer 22. The opening OP may have a mesh structure in a plan view. As described with reference to Figs. 1 to 3, the opening OP may have a grid shape in plan view, for example. In detail, the opening OP may include first openings OP1 extending in the X-direction and forming a plurality of rows and second openings OP2 extending in the Y-direction to form a plurality of rows .

5 and 9, a metal pattern 30 may be formed in the opening OP (S40). The metal pattern 30 may be formed through a plating process. For example, the plating process may include a metal electro-less plating process or a metal electroplating process. During the plating process of the metal pattern 30, the source material used for the plating process may be deposited only on the upper surface of the exposed metal layer 22, and may not be deposited on the mask pattern M. For example, in the case of the electroless plating process, the upper surface of the exposed metal layer 22 may serve as a seed. That is, the upper surface of the exposed metal layer 22 may increase the uniformity of the metal pattern 30 to be plated and may serve as an initial nucleation site. For example, in the case of the electroplating process, metal ions may be deposited on the exposed upper surface of the metal layer 22 by the potential applied to the metal layer 22. [ The source material used in the plating process for forming the metal pattern 30 may include copper (Cu), nickel (Ni), silver (Ag), or an alloy thereof. The metal pattern 30 may be filled from the bottom of the opening OP by a plating process. In other words, the opening OP and the mask pattern M may serve as a mold for filling the metal pattern 30. The metal pattern 30 may be formed to have a second height h2 from the top surface of the second oxide layer 23. [ The second height h2 may be between 0.1 and 10 micrometers. At this time, the second height h2 may be smaller than the first height h1. That is, the metal pattern 30 may not protrude above the upper surface of the mask pattern M. This is to maintain the planar structure in which the metal pattern 30 is defined by the opening OP during the plating process of the metal pattern 30. [ When the metal pattern 30 is plated so as to protrude from the upper surface of the mask pattern M, the metal pattern 30 is grown so as to spread in a plane on the mask pattern M.

Since the metal pattern 30 according to the embodiments of the present invention is formed by filling the opening OP, the metal pattern 30 may have substantially the same planar structure as the opening OP. That is, the planar structure of the metal pattern 30 is determined by the planar structure of the opening OP, and this allows adjustment of the planar structure of the metal pattern 30 through patterning of the mask pattern M forming the opening OP . For example, as described with reference to Figs. 1 to 3, when the opening OP has a grid shape in a plan view, the metal pattern 30 may be formed in a planar grid shape have. At this time, the width and the interval of the metal pattern 30 may correspond to the width and the distance of the openings OP. According to another embodiment, the metal pattern 30 may have various planar structures defined by the openings OP. 4, the opening OP of the second oxide layer 23 may have a honeycomb-type mesh structure, and correspondingly, the metal pattern 30 may also have a honeycomb structure, (honeycomb) shape.

Referring to Figs. 5 and 10, the mask pattern M can be removed (S50). For example, the mask pattern M may be removed through an ashing process. Due to the removal of the mask pattern M, the top surface of the second oxide layer 23 can be exposed.

Referring again to Fig. 1, a protective layer 40 may be formed on the second oxide layer 23 and the metal pattern 30. [ The protective layer 40 may be formed through a process such as spin on glass (SOG) or plasma enhanced chemical vapor deposition (PECVD). At this time, the upper surface of the protective layer 40 may be higher than the upper surface of the metal pattern 30. That is, the protective layer 40 may be formed to cover the second oxide layer 23 and the metal pattern 30. The protective layer 40 may comprise silicon oxide (SiO2). According to another embodiment, the process of forming the protective layer 40 may be omitted if necessary.

The transparency and the sheet resistance of the transparent electrode according to the width, spacing and height of the metal pattern 30 were simulated. 11 is a table showing simulation results of transparency and sheet resistance of a transparent electrode according to embodiments of the present invention.

In this simulation, it is assumed that the transparent substrate 10 is formed of glass and the metal pattern 30 is formed of copper (Cu). At this time, the specific resistance of copper (Cu) is 1.72410? 7 ?. The first width w1 of the first metal patterns 31 forming the metal pattern 30 and the second width w2 of the second metal patterns 32 are the same and the first metal patterns 31 31 are spaced apart from each other and the second distance d2 from which the second metal patterns 32 are spaced apart are assumed to be the same.

11, line with represents the width of the first metal patterns 31 and the second metal patterns 32, and pitch represents the distance between the first and second metal patterns 31 and 32 And the thickness indicates the second height h2 that the metal pattern 30 protrudes from the upper surface of the second oxide layer 23. [ T represents the transmittance of the transparent electrode, and Rs represents the sheet resistance of the transparent electrode. From the simulation results, it can be seen that the transparent electrode has a transmittance of 89 to 91.5% and a sheet resistance of 0.1724 to 1.2792? / ?.

In other embodiments, the transparent electrode further comprises an adhesion layer between the first oxide layer 21 and the metal layer 22 or between the metal layer 22 and the second oxide layer 23, The adhesion between the first and second oxide layers 21 and 23 and the metal layer 22, the thermal stability at a high temperature, and the uniformity of the plating in the metal pattern plating process can be improved. Here, for the sake of convenience of explanation, the points which are different from or different from those described above will be mainly described, and the omitted parts are based on the above-described contents of the present invention.

12 is a cross-sectional view for explaining a modification of the transparent electrode according to the embodiments of the present invention. 12, a first oxide layer 21, a first adhesive layer AL1, a metal layer 22, a second adhesive layer AL2, and a second oxide layer 23 are sequentially formed on a transparent substrate 10 The multilayer transparent conductive film 20 can be formed. For example, the adhesive layer may be formed by a physical vapor deposition (PVD) method, a CVD (chemical vapor deposition) method or a chemical vapor deposition (CVD) method together with the first oxide layer 21, the metal layer 22 and the second oxide layer 23 in the process of forming the multilayer transparent conductive film 20. [ a chemical vapor deposition method or a sputtering method. The first and second adhesive layer (AL1, AL2) is aluminum (Al), titanium (Ti), chromium (Cr), aluminum nitride (AlN), titanium nitride (TiN), aluminum oxide (Al 2 O 3), titanium oxide (TiO 2 ), chromium oxide (Cr 2 O 3 ), or silicon oxide (SiO 2 , Si 3 O 4 ). The first and second adhesive layers AL1 and AL2 may have a thickness of 0.5 to 10 nanometers. 11, the first adhesive layer AL1 and the second adhesive layer AL2 are all included, but the transparent electrode may include only one of the first adhesive layer AL1 and the second adhesive layer AL2 .

A mask pattern M can be formed on the second oxide layer 23. [ The mask pattern M may be, for example, a photo resist pattern. For example, the mask pattern M may be formed by applying a photoresist on the second oxide layer 23, exposing the photoresist, and developing the exposed photoresist.

Thereafter, the opening OP can be formed in the multilayer transparent conductive film 20. The opening OP may be formed by etching the second oxide layer 23 using the mask pattern M as a mask. The opening OP formed in the second oxide layer 23 may expose a part of the upper surface of the second adhesive layer AL2 rather than the metal layer 22. [ The opening OP may have a mesh structure in a plan view.

The metal pattern 30 may be formed in the opening OP. The metal pattern 30 may be formed through a plating process. The source material used in the plating process can be deposited only on the upper surface of the exposed second adhesive layer AL2. That is, the metal pattern 30 may be formed on the upper surface of the exposed second adhesive layer AL2. At this time, the second adhesive layer AL2 may have the same role as the metal layer 22 in the above-described plating process.

The mask pattern M can be removed. For example, the mask pattern M may be removed through an ashing process. Due to the removal of the mask pattern M, the top surface of the second oxide layer 23 can be exposed.

The protective layer 40 may be formed on the second oxide layer 23 and the metal pattern 30. The protective layer 40 may be formed through a process such as spin on glass (SOG) or plasma enhanced chemical vapor deposition (PECVD). At this time, the protective layer 40 may be formed to cover the second oxide layer 23 and the metal pattern 30.

In still another embodiment, the method of manufacturing a transparent electrode further includes a step of forming an oxidation-preventive film on the metal pattern 30, thereby preventing oxidation of the metal pattern 30. Here, for the sake of convenience of explanation, the points which are different from or different from those described above will be mainly described, and the omitted parts are based on the above-described contents of the present invention.

13 is a cross-sectional view for explaining another modification of the transparent electrode according to the embodiments of the present invention. Referring to FIG. 13, the multilayer transparent conductive film 20 can be formed on the transparent substrate 10. The multilayer transparent conductive film 20 may be formed by sequentially laminating a first oxide layer 21, a metal layer 22 and a second oxide layer 23 on a transparent substrate 10. For example, each of the first oxide layer 21, the metal layer 22 and the second oxide layer 23 may be formed using a physical vapor deposition (PVD) method, a chemical vapor deposition (CVD) method, or a sputtering method .

A mask pattern M can be formed on the second oxide layer 23. [ The mask pattern M may be, for example, a photo resist pattern. For example, the mask pattern M may be formed by applying a photoresist on the second oxide layer 23, exposing the photoresist, and developing the exposed photoresist.

The opening OP can be formed in the multilayer transparent conductive film 20. [ The opening OP may be formed by etching the second oxide layer 23 using the mask pattern M as a mask. At this time, the opening OP may expose the upper surface of the metal layer 22. The opening OP may have a mesh structure in a plan view.

The metal pattern 30 may be formed in the opening OP. The metal pattern 30 may be formed through a plating process. For example, the plating process may include a metal electro-less plating process or a metal electroplating process. During the plating process of the metal pattern 30, the source material used for the plating process may be deposited only on the upper surface of the exposed metal layer 22, and may not be deposited on the mask pattern M.

An oxidation preventing film 35 may be formed on the metal pattern 30. The oxidation preventing film 35 may be formed through a plating process. For example, after the plating process for forming the metal pattern 30, a plating process for forming the oxidation preventive film 35 can be continuously performed. The oxidation preventing film 35 may be formed so as to cover the metal pattern 30. The oxidation preventing film 35 may include nickel (Ni) or silver (Ag). The step of forming the oxidation preventing film 35 may be performed when the metal pattern 30 is formed of a metal that is easily oxidized, such as copper (Cu).

The protective layer 40 may be formed on the second oxide layer 23 and the oxidation preventing film 35. [ The protective layer 40 may be formed through a process such as spin on glass (SOG) or plasma enhanced chemical vapor deposition (PECVD). At this time, the protective layer 40 may be formed to cover the second oxide layer 23 and the oxidation preventing film 35.

In one embodiment, the process of coating the oxidation prevention film 35 is performed after the metal pattern 30 is formed. However, the process of coating the oxidation prevention film 35 may be performed after removing the mask pattern M It is possible.

A method of forming a metal mesh of a mesh structure using a conventional plating process includes forming a metal seed layer on a substrate and then performing an electroless plating process on the metal seed layer. However, the conventional method has a limitation in reducing the line width of the metal seed layer.

In the method of manufacturing a transparent electrode according to embodiments of the present invention, the second oxide layer can be patterned with a very fine line width of several nanometers by the nature of a photolithography process, To form a metal pattern. Therefore, a metal pattern having a fine line width can be formed by patterning the mask pattern. The metal pattern of a mesh having fine line widths of several nanometers can exhibit very good transmittance and can reduce optical moiré and star burst. In addition, since a simple patterning process and a plating process are used, it is easy to manufacture a large-area transparent electrode.

The transparent electrode fabricated through embodiments of the present invention has a metal pattern of a mesh structure having a fine line width on a multilayer transparent conductive film of an oxide / metal / oxide (OMO) structure. Therefore, the transparent electrode can secure the low resistance property by the metal pattern while maintaining the high transmittance of the multilayer transparent conductive film, and improve the resistance uniformity of the metal pattern.

The transparent electrode described above can be applied to a transparent heater. The transparent electrode to which the above-described technique of the present invention is applied can be provided as a heating portion of the transparent heater. 14 is a cross-sectional view showing an example of a transparent heater to which a transparent electrode according to embodiments of the present invention is applied. 15 is an exploded perspective view showing an example of a bonded glass for a vehicle to which a transparent electrode according to embodiments of the present invention is applied.

Referring to FIG. 14, the transparent heater 100 may include a first transparent substrate 110, an electrode terminal portion 120, and a heat generating portion 130. The heating portion 130 may include a transparent electrode according to embodiments of the present invention. The heat generating portion 130 may be disposed on the first transparent substrate 110. The electrode terminal portion 120 is formed on one side of the first transparent substrate 110 and may be electrically connected to the heat generating portion 130. At this time, the electrode terminal unit 120 is electrically connected to the external power source S, and can supply power to the heat generating unit 130. The heat generating unit 130 is electrically connected to the electrode terminal unit 120 and can receive power from the external power source S and generate heat according to the electric resistance. Referring to FIG. 15, when the transparent heater according to the present invention is a bonded glass for an automobile, a poly vinyl butyral (PVB) film 140 may be disposed on the heat generating part 130. The PVB film 140 may be provided to improve stability. The second transparent substrate 150 may be disposed on the PVB film 140. Either one of the first transparent substrate 110 and the second transparent substrate 150 may be an inner glass in an automotive laminated glass and the other may be an outer glass.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: transparent substrate 20: multilayer transparent conductive film
21: first oxide layer 22: metal layer
23: second oxide layer 30: metal pattern
40: Protective layer
M: mask pattern OP: opening

Claims (17)

A method of forming a multilayer transparent conductive film on a transparent substrate, the multilayer transparent conductive film comprising a first oxide layer, a metal layer, and a second oxide layer sequentially laminated on the transparent substrate;
Forming a mask pattern on the second oxide layer;
Performing an etch process using the mask pattern as an etch mask to form a trench in the second oxide layer, the trench exposing an upper surface of the metal layer; And
And forming a metal pattern in the trench. The method according to claim 1,
Wherein the metal pattern has a mesh structure in plan view. 3. The method of claim 2,
The metal pattern may include a first metal pattern extending in one direction in a planar manner and forming a plurality of rows, and a second metal pattern extending in a direction perpendicular to the first direction, Gt; 3. The method of claim 2,
Wherein the metal pattern has a honeycomb shape in plan view. The method according to claim 1,
The formation of the metal pattern may be performed,
And performing a plating process using an upper surface of the exposed metal layer as a seed. 6. The method of claim 5,
In the plating step,
Wherein at least one selected from the group consisting of copper (Gu), nickel (Ni), silver (Ag), and alloys thereof is used as a source material. The method according to claim 1,
Wherein the upper surface of the metal pattern is formed to be higher than the upper surface of the second oxide layer and lower than the upper surface of the mask pattern. 8. The method of claim 7,
Wherein the mask pattern has a height of 1 to 10 micrometers from one surface of the second oxide layer,
Wherein the metal pattern has a height of 0.1 to 10 micrometers from one surface of the second oxide layer. The method according to claim 1,
Wherein the metal pattern has a width of 1 to 20 micrometers. The method according to claim 1,
The metal layer may be any one selected from the group consisting of silver (Ag), aluminum (Al), molybdenum (Mo), gold (Au), palladium (Pd), titanium (Ti), copper Wherein the transparent electrode is a transparent electrode. The method according to claim 1,
Each of the first oxide layer and the second oxide layer is zinc oxide (ZnO), tin oxide (SnO2), silicon oxide (SiO 2), titanium oxide (TiO 2), silicon nitride (SiN x), ZITO (ZnO + In 2 O 3 + SnO 2 ), ZTO (ZnO + SnO 2), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ITO (In 2 O 3 + SnO 2), IZO (In 2 O 3 + ZnO), and a compound of any of the foregoing. The method according to claim 1,
Wherein the multilayer transparent conductive film further comprises an adhesive layer,
The adhesive layer comprises:
Wherein the transparent electrode is formed on at least one of the first oxide layer and the metal layer and between the metal layer and the second oxide layer. 13. The method of claim 12,
The adhesive layer of aluminum (Al), titanium (Ti), chromium (Cr), aluminum nitride (AlN), titanium nitride (TiN), aluminum oxide (Al 2 O 3), titanium oxide (TiO 2), chromium oxide (Cr 2 O 3 ), and silicon oxide (SiO 2 , Si 3 O 4 ). The method according to claim 1,
After forming the metal pattern,
And forming an oxidation preventing film on the metal pattern. 15. The method of claim 14,
Wherein the oxidation preventing film comprises nickel (Ni) or silver (Ag). The method according to claim 1,
After removing the mask pattern,
And forming a protective layer to cover the second oxide layer and the metal pattern. 17. The method of claim 16,
Wherein the protective layer comprises silicon oxide (SiO2).
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