KR20150042369A - Hybrid transparent electrode and the fabricating method thereof - Google Patents

Abstract

Provided by the present invention are a hybrid transparent electrode and a manufacturing method thereof. For the aforementioned, the present invention provides a metal mesh and a silver nanowire hybrid transparent electrode which include a metal mesh layer and a silver nanowire layer on a transparent substrate. The hybrid transparent electrode manufacturing method provided by the present invention includes: a step 1 of forming a metal mesh layer on a transparent substrate; and a step 2 of forming a silver nanowire layer by growing the silver nanowire on the metal mesh layer formed on the transparent substrate. The present invention is able to: solve a visibility problem causing a metal mesh layer to be exposed by forming a silver nanowire layer on the metal mesh layer having a fine line width; and compensate the degradation of conductivity generated by the fine line width using the silver nanowire layer. The present invention is able to solve a haze problem caused by a nanowire layer by forming a silver nanowire layer in a proper thickness since conductivity can be improved by forming a metal mesh layer and the silver nanowire layer at the same time. Thereby a transparent electrode can be manufactured in an environmentally friendly manner since a chemical process is not used in a process of forming the transparent electrode.

Description

[0001] Hybrid transparent electrodes and fabrication methods [

The present invention relates to a hybrid transparent electrode and a method for manufacturing the same.

Recently, a transparent electrode substrate having a transparent conductive layer has been actively studied in various solar cells including organic electroluminescence (organic EL), organic solar cells, touch panels, cellular phones, and electronic paper. BACKGROUND ART A transparent electrode substrate having a transparent conductive layer formed on a substrate such as a glass substrate is generally used as an electrode of an electronic device such as a solar cell or an organic EL device.

Most of the transparent electrodes used in the industry today are ITO, and ITO is a material prepared by dissolving tin oxide (SnO ₂ ) in indium oxide (In ₂ O ₃ ). ITO is an oxide which is stable at room temperature and exhibits optical characteristics in the visible light region, reflectance characteristic in the infrared region, and has relatively low electric resistance, and is mostly used in the transparent electrode portion of the touch panel, LCD, and OLED.

Accordingly, the price of indium has been continuously rising due to the scarcity of indium. In 2003, the annual average price of indium was only $ 87 per kg, but in 2004, it rose to an annual average of $ 1,489. This is due to the surge in demand for indium tin oxide (ITO), the largest demand for indium. That is, the use of ITO as the conductive layer of the transparent electrode has a problem that the unit cost for manufacturing the transparent electrode increases.

In addition, a transparent electrode substrate using a metal oxide layer such as an ordinary ITO as a transparent conductive layer is not low in surface resistivity, and the volume resistivity of ITO itself is also high. As a transparent conductive substrate such as an organic EL, various solar cells, a touch panel, a cellular phone, and an electronic paper, a transparent conductive substrate having a surface resistivity of about 5? /? Or less, for example, is required. To such a demand, a transparent electrode substrate using a metal material layer having an extremely lower volume resistivity than the transparent conductive layer as an auxiliary electrode has been studied.

For example, Patent Document 1 discloses a substrate with a transparent conductive film in which a transparent oxide layer, a metal layer, and a transparent oxide layer are laminated in this order on a substrate. However, such a structure has a low light transmittance and is not practical as a transparent electrode substrate of a thin film device. Further, since the metal layer is laminated on the entire surface of the transparent oxide layer, the durability of the thin film device using the gas with the transparent conductive film may be a problem due to deterioration of the metal layer.

In Patent Document 2, a stripe-shaped or mesh-shaped auxiliary electrode layer made of a metal is formed on a first electrode made of ITO formed on a substrate, a light emitting layer for fixing a light emitting region thereon, and a second electrode formed thereon An electroluminescent panel is disclosed.

Further, Patent Document 3 discloses a light emitting device having a transparent electrode and a transparent electrode, a mesh electrode and a transparent electrode made of a metal thin film which are sequentially stacked on the transparent substrate, a photoelectric conversion layer formed on the mesh electrode and the transparent electrode, An organic thin film solar cell having an opposite electrode is disclosed. However, in such a structure, there is a possibility that problems such as deterioration due to corrosion of the metal may occur.

Patent Document 4 discloses a transparent conductive film having a transparent conductive layer composed of a conductive metal mesh layer made of an alloy made of a base metal or a nonmetal and a conductive polymer layer on at least one surface of a transparent substrate sheet, Discloses a transparent conductive film having a mesh-like conductive layer formed on at least one kind of metal on a transparent support, wherein a transparent conductive layer containing a migration inhibitor is provided on the conductive layer And Patent Document 6 discloses an electrode for a dye-sensitized solar cell in which a transparent conductive film is formed on a substrate. In the electrode for a dye-sensitized solar cell, an electrode for a dye sensitized solar cell provided with a conductor having a resistance lower than that of the transparent conductive film is provided between the substrate and the transparent conductive film .

In addition to the above-described methods, further improvement of transparency, conductivity, and durability is required for transparent electrode substrates as electrodes of electronic devices such as solar cells and organic EL devices.

For this purpose, the inventors of the present invention have been studying a novel transparent electrode capable of replacing the conventional ITO transparent electrode. When manufacturing the hybrid transparent electrode of the metal mesh and the silver nanowire, the inventors of the present invention supplemented the drawbacks of the metal mesh and the silver nanowire And thus a transparent electrode having excellent performance can be produced. Thus, the present invention has been completed.

Japanese Unexamined Patent Publication No. 10-241464 Japanese Patent Laid-Open No. 2008-103305 Japanese Patent Application Laid-Open No. 2010-157681 Japanese Patent Application Laid-Open No. 2009-081104 Japanese Patent Laid-Open No. 2009-146678 Japanese Patent Application Laid-Open No. 2004-296669

It is an object of the present invention to provide a hybrid transparent electrode and a method of manufacturing the same.

To this end,

A hybrid transparent electrode of metal mesh and silver nanowire is provided, which comprises a metal mesh layer and a silver nanowire layer on a transparent substrate.

In addition,

Forming a metal mesh layer on the transparent substrate (step 1); And

Forming a silver nanowire layer on the metal mesh layer formed on the transparent substrate (step 2);

The present invention also provides a method of manufacturing a hybrid transparent electrode.

In addition,

Forming a silver nanowire layer on the transparent substrate (step 1); And

Forming a metal mesh layer on the silver nanowire layer formed on the transparent substrate (step 2);

The present invention also provides a method of manufacturing a hybrid transparent electrode.

Further, the present invention provides an electronic device including the hybrid transparent electrode.

In the present invention, the problem of visibility that the metal mesh layer is visible by forming a silver nanowire layer on the metal mesh layer having a fine line width is solved, and the deterioration of the electrical conductivity caused by the fine line width is supplemented with the silver nanowire layer can do. In addition, since the metal mesh layer and the silver nanowire layer are simultaneously formed, the electrical conductivity can be improved, so that the silver nanowire layer can be formed to have an appropriate thickness, thereby solving the haze problem caused by the nanowire layer have. Furthermore, since a chemical process may not be used in the process for forming the transparent electrode, the transparent electrode can be produced environmentally.

1 is a schematic view showing a method of manufacturing a hybrid transparent electrode according to Embodiment 1 of the present invention;
2 is a schematic view of a metal mesh formed on a transparent substrate;
3 is a graph showing a theoretical surface resistance value according to the pitch of the metal mesh;
4 is an image showing a laser irradiation method, which is a kind of method of forming a metal mesh;
5 is an image showing a change in linewidth of a metal mesh according to a laser irradiation condition in a method of forming a metal mesh;
FIG. 6 is a graph showing transmittance according to a wavelength in a pitch change of a metal mesh having a line thickness of 5 - 6 μm; FIG.
FIG. 7 is a graph showing transmittance according to a wavelength in a pitch change of a metal mesh having a line thickness of 3 - 4 μm; FIG.
FIG. 8 is a graph showing transmittance according to wavelengths in changes in sheet resistance of silver nanowires; FIG.
9 is a schematic view showing a method of manufacturing a hybrid transparent electrode according to Embodiment 7 of the present invention;
10 is an image obtained by observing the transparent electrode prepared in Comparative Example 1 (left) and Example 1 (right) of the present invention with a scanning electron microscope;
11 is a schematic view showing the transmittance and sheet resistance of the transparent electrode prepared in Example 2 of the present invention and Comparative Examples 1 and 3;
12 is a graph showing the transmittance and sheet resistance of the transparent electrode prepared in Examples 2 to 6 of the present invention.

The present invention

A hybrid transparent electrode characterized by comprising a metal mesh layer and a silver nanowire layer on a transparent substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The hybrid transparent electrode according to the present invention includes a metal mesh layer on a transparent substrate.

At this time, it is preferable that the transparent substrate has a total light transmittance of 85% or more from the viewpoint of transparency. As such a transparent substrate, a glass plate or a plastic film can be generally used.

Examples of the plastic film include polyethyleneterephthalate, polyethylene naphthalate, triacetylcellulose, syndiotactic polystyrene, polyphenylene sulfide, polycarbonate, polyallylate, polysulfone, polyester sulfone, poly A plastic film made of an ether imide, a cyclic polyolefin, or the like. Among them, it is more preferable to use a plastic film made of glass (plate), polyethylene terephthalate, polyethylene naphthalate, polyallylate or the like, which is excellent in mechanical strength, durability, transparency and versatility. The thickness of the transparent substrate is preferably 3 탆 to 5 탆, more preferably 5 탆 to 3 탆, and particularly preferably 10 탆 to 1 관점m from the viewpoint of balance of mechanical strength, durability and transparency.

The metal mesh layer is formed on the transparent substrate to serve as a transparent conductive layer. The shape of the metal mesh layer has an opening, and its shape is not particularly limited. For example, it can be used as a mesh shape having a periodicity such as a square, a rectangle, and a hexagon as shown in Fig.

The following equations (1) and (2) are calculation formulas for obtaining the theoretical sheet resistance and permeability of the metal mesh layer. The sheet resistance and permeability can be predicted theoretically by considering the filling factor in the equation for calculating the sheet resistance Therefore, the design of the metal mesh can be performed. The peeling factor means the ratio of the metal wire width to the sum of the metal wire width and the wire width of the metal mesh layer, which is obtained as follows (see FIG. 2).

Filling factor (f _F ) = W / (G + W)

Here, W represents the line width of the metal line forming the metal mesh layer, and G represents the metal line interval of the metal mesh layer.

&Quot; (1) "

&Quot; (2) "

Where? Is the correction coefficient, t _G is the thickness of the metal wire,? _G is the resistivity, and f _F is the filling factor.

According to Equations (1) and (2), when the width of the metal wire composing the metal mesh layer is reduced or the distance between the metal wires is increased, the value of the fill factor is decreased. In such a case, But the permeability is improved. That is, it can be seen that the width and the interval of the metal line forming the metal mesh layer affect the electrical conductivity and the transmittance of the transparent electrode.

In the hybrid transparent electrode according to the present invention, it is preferable that the width of the metal line constituting the metal mesh layer is 100 탆 which is 1 탆, and the interval between the metal lines is 300 탆 to 2000 탆 (see analysis 1 and analysis 2).

When the width of the metal wire is less than 1 탆, there is a problem that the metal wire forming the metal mesh layer is washed out during the washing process after the metal mesh layer is formed. When the width exceeds 100 탆, the line width becomes thick, Visible visibility problems may appear.

At this time, the width of the metal mesh layer is more preferably 1 탆 to 5 탆, and still more preferably 3 탆 to 4 탆. In the case of the metal mesh having such a fine line width, better transmittance can be obtained under the same conditions.

When the distance between the metal wires is less than 300 탆, the pattern of the metal mesh layer may have visible visibility. If the distance exceeds 2000 탆, the permeability may be improved, but the sheet resistance of the metal mesh layer may increase, There is a possibility that a problem of deterioration may occur.

For example, according to FIG. 3, the mesh interval of a metal mesh transparent electrode having a thickness of 200 nm and a line width of 5 탆 has a problem in that the sheet resistance increases as the pitch increases and the electrical conductivity decreases, have.

In the hybrid transparent electrode according to the present invention, the metal mesh layer may be at least one selected from the group consisting of gold, silver, copper, aluminum, titanium, chromium, iron, cobalt, nickel, zinc, tin, iridium, indium, tungsten, molybdenum, platinum, iridium, hafnium , Niobium, tantalum, tungsten, and magnesium, but it is not particularly limited as long as it is a metal or alloy having conductivity.

Of these, metal of gold, silver, copper, platinum, aluminum, titanium, nickel and chromium having high corrosion resistance and high conductivity is preferable and is selected from the group consisting of gold, silver, copper, platinum, aluminum, nickel and chromium It is more preferable to use at least one of them.

Examples of the alloy include compounds which are metals such as stainless steel, nickel-chromium, Inconel (trade name), bronze, phosphor bronze, brass, duralumin, white copper, drawn, monel and nickel phosphorus alloys; metal boron compounds such as nickel boron; Metal nitride and the like. In particular, an alloy mainly composed of copper, an alloy mainly composed of nickel, an alloy mainly composed of cobalt, an alloy mainly composed of chromium, and an alloy mainly composed of aluminum are preferable because they are excellent in conductivity and workability have.

The conductive metal mesh layer may be a single layer made of a metal or an alloy, or a multi-layered structure in which layers made of at least two kinds of metals or alloys are laminated.

In the hybrid transparent electrode according to the present invention, the thickness of the metal mesh layer is preferably 200 nm to 500 nm. When the thickness of the metal mesh layer is less than 200 nm, the metal mesh layer has a low conductivity. When the thickness of the metal mesh layer is more than 500 nm, the thickness of the transparent electrode is increased. have.

The hybrid transparent electrode according to the present invention includes a silver nanowire layer together with the metal mesh layer.

According to the present invention, since the metal mesh layer formed on the transparent substrate can have a fine line width, the transmittance can be improved, but the sheet resistance increases and the electric conductivity decreases. Therefore, when the silver nanowire layer is formed on the transparent substrate on which the metal mesh layer is formed, a transparent electrode can be manufactured which complements the electrical conductivity reduced due to the fine line width and exhibits sufficient electrical performance. At this time, the silver nanowire layer has to form a silver nanowire layer having low sheet resistance in order to exhibit excellent electrical conductivity, and haze is generated in such a case.

For example, according to FIG. 4, as the thickness of the nanowire layer increases, the sheet resistance of silver nanowires may decrease, but haze occurs and the transmittance decreases.

Accordingly, in the present invention, a visibility problem in which a metal mesh layer is visible by forming a silver nanowire layer on a metal mesh layer having a fine line width is solved, and a decrease in electrical conductivity caused by a fine line width is called a silver nanowire layer . In addition, since the metal mesh layer and the silver nanowire layer are simultaneously formed, the electrical conductivity can be improved, so that the silver nanowire layer can be formed to have an appropriate thickness, thereby solving the haze problem caused by the nanowire layer have. Furthermore, since a chemical process may not be used in the process for forming the transparent electrode, the transparent electrode can be produced environmentally.

In addition,

Forming a metal mesh layer on the transparent substrate (step 1); And

Forming a silver nanowire layer on the metal mesh layer formed on the transparent substrate (step 2);

The present invention also provides a method of manufacturing a hybrid transparent electrode.

Hereinafter, the present invention will be described in detail by steps.

In the method of manufacturing a hybrid transparent electrode according to the present invention, the step 1 is a step of forming a metal mesh layer on a transparent substrate.

At this time, it is preferable that the transparent substrate has a total light transmittance of 85% or more from the viewpoint of transparency. As such a transparent substrate, a glass plate or a plastic film can be generally used.

Examples of the plastic film include polyethyleneterephthalate, polyethylene naphthalate, triacetylcellulose, syndiotactic polystyrene, polyphenylene sulfide, polycarbonate, polyallylate, polysulfone, polyester sulfone, poly A plastic film made of an ether imide, a cyclic polyolefin, or the like. Among them, it is more preferable to use a plastic film made of glass (plate), polyethylene terephthalate, polyethylene naphthalate, polyallylate or the like, which is excellent in mechanical strength, durability, transparency and versatility. The thickness of the transparent substrate is preferably 3 to 5 mm, more preferably 5 to 3 mm, and particularly preferably 10 to 1 mm from the viewpoint of balance of mechanical strength, durability and transparency.

In the method for manufacturing a hybrid transparent electrode according to the present invention, it is preferable that a width of a metal line constituting the metal mesh layer is 100 탆 which is 1 탆, and a distance between metal lines is 300 탆 to 2000 탆.

When the width of the metal wire is less than 1 탆, there is a problem that the metal wire forming the metal mesh layer is washed out during the washing process after the metal mesh layer is formed. When the width exceeds 100 탆, the line width becomes thick, Visible visibility problems may appear.

At this time, the width of the metal mesh layer is more preferably 1 탆 to 5 탆, and still more preferably 3 탆 to 4 탆. In the case of the metal mesh having such a fine line width, better transmittance can be obtained under the same conditions.

When the distance between the metal wires is less than 300 탆, the pattern of the metal mesh layer may have visible visibility. If the distance exceeds 2000 탆, the permeability may be improved, but the sheet resistance of the metal mesh layer may increase, There is a possibility that a problem of deterioration may occur.

For example, according to FIG. 3, the mesh interval of a metal mesh transparent electrode having a thickness of 200 nm and a line width of 5 탆 has a problem in that the sheet resistance increases as the pitch increases and the electrical conductivity decreases, have.

In the method of manufacturing a hybrid transparent electrode according to the present invention, the metal mesh layer may be formed of a metal such as gold, silver, copper, aluminum, titanium, chromium, iron, cobalt, nickel, zinc, tin, iridium, indium, tungsten, molybdenum, Iridium, hafnium, niobium, tantalum, tungsten, and magnesium, but it is not particularly limited as long as it is a metal or alloy having conductivity.

Of these, metal of gold, silver, copper, platinum, aluminum, titanium, nickel and chromium having high corrosion resistance and high conductivity is preferable and is selected from the group consisting of gold, silver, copper, platinum, aluminum, nickel and chromium It is more preferable to use at least one of them.

Examples of the alloy include compounds which are metals such as stainless steel, nickel-chromium, Inconel (trade name), bronze, phosphor bronze, brass, duralumin, white copper, drawn, monel and nickel phosphorus alloys; metal boron compounds such as nickel boron; Metal nitride and the like. In particular, an alloy mainly composed of copper, an alloy mainly composed of nickel, an alloy mainly composed of cobalt, an alloy mainly composed of chromium, and an alloy mainly composed of aluminum are preferable because they are excellent in conductivity and workability have.

The conductive metal mesh layer may be a single layer made of a metal or an alloy, or a multi-layered structure in which layers made of at least two kinds of metals or alloys are laminated.

In the method of manufacturing a hybrid transparent electrode according to the present invention, the thickness of the metal mesh layer is preferably 200 nm to 500 nm. When the thickness of the metal mesh layer is less than 200 nm, the metal mesh layer has a low conductivity. When the thickness of the metal mesh layer is more than 500 nm, the thickness of the transparent electrode is increased. have.

At this time, the method of forming the metal mesh as the transparent conductive layer on the transparent substrate is not particularly limited, and a known method can be used. For example, the material of these transparent conductive layers is subjected to a dry process such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, or CVD (chemical vapor deposition) such as thermal CVD or atomic layer deposition (ALD) , Or a wet process, such as an inkjet method or a screen printing method, and is appropriately selected depending on the material of the transparent substrate or the transparent conductive layer.

However, it is more preferable that the metal mesh layer is formed through a patterning process using a laser. According to the conventional method of forming a metal mesh by etching a metal thin film, it is difficult to realize such a fine line width. However, according to the patterning process using the laser, it is possible to form a metal line having a fine line width of 1 탆 to 5 탆 and to improve the permeability of the metal mesh.

Specifically, the metal mesh layer may be formed by forming a metal organic ink layer on a transparent substrate in a semi-solid form, curing the metal organic layer by laser irradiation, and then washing the metal organic layer to form a metal mesh layer.

In the method of manufacturing a hybrid transparent electrode according to the present invention, the step 2 is a step of forming a silver nanowire layer on the metal mesh layer formed on the transparent substrate.

In the present invention, since the metal mesh layer formed on the transparent substrate can have a fine line width, the transmittance can be improved, but the sheet resistance rises and the electrical conductivity decreases. Therefore, when a silver nanowire layer is formed on the transparent substrate on which the metal mesh layer is formed, a transparent electrode having sufficient electrical performance can be manufactured by supplementing the electrical conductivity reduced due to the fine line width. At this time, the silver nanowire layer should have a silver nanowire layer so as to have a low sheet resistance in order to exhibit excellent electrical conductivity. Generally, a thicker silver nanowire layer should be formed, so that haze there is a problem.

Accordingly, in the present invention, a visibility problem in which a metal mesh layer is visible by forming a silver nanowire layer on a metal mesh layer having a fine line width is solved, and a decrease in electrical conductivity caused by a fine line width is called a silver nanowire layer . In addition, since the metal mesh layer and the silver nanowire layer are simultaneously formed, the electrical conductivity can be improved, so that the silver nanowire layer has appropriate sheet resistance and the thickness of the silver nanowire layer, It is possible to solve the haze problem that occurs. Furthermore, since a chemical process may not be used in the process for forming the transparent electrode, the transparent electrode can be produced environmentally.

The silver nanowire layer may be formed by one method selected from the group consisting of spin coating, spray coating, dip coating and roll-to-roll coating. And it is not particularly limited as long as it is a method capable of forming a silver nanowire layer on a substrate to produce a transparent electrode.

In the method of manufacturing a hybrid transparent electrode according to the present invention, when the silver nanowire layer is formed by a method using spin coating, the rotation speed is preferably 500 rpm to 4000 rpm. In the case of less than 500 rpm, the transmittance is lowered and a haze problem may occur. If it exceeds 4000 rpm, there is a problem that the sheet resistance of the silver nanowire layer produced by the above method becomes excessively large and the electric conductivity is lowered.

In addition,

Forming silver nanowires on the transparent substrate (step 1); And

Forming a metal mesh layer on the transparent substrate on which the silver nanowires are formed (step 2);

And a method of manufacturing a hybrid transparent electrode of a silver nanowire.

The manufacturing method of the hybrid transparent electrode of the metal mesh and the silver nanowire can use the same method except that the order of steps 1 and 2 is changed in the manufacturing method presented above (refer to FIG. 9).

Further, the present invention provides an electronic device including the transparent electrode. Examples of the electronic device to which the transparent electrode of the present invention can be applied include devices such as a transistor, a memory, an organic EL, and a solar cell, a liquid crystal display, an electronic paper, a thin film transistor, an electrochromic, an electrochemiluminescent device, A photoelectric conversion device, a thermoelectric conversion device, a piezoelectric conversion device, and an electric storage device.

As the solar cell to which the transparent electrode of the present invention can be applied, an organic thin film solar cell, a thin film silicon solar cell, a hybrid solar cell, a multi-junction solar cell, a spherical silicon solar cell, a field effect solar cell, Dye-sensitized solar cells, and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

≪ Example 1 >

Step 1: The organic silver compound was spin-coated on a transparent substrate at 4000 rpm and heat-treated at a temperature of 100 ° C for 60 seconds to form fine nanoparticles.

The material was irradiated at a power of 0.2 W through a laser direct patterning (LDP) method to form a metal mesh layer having a fine line width of 3 to 6 μm and a pitch of 300 μm.

Step 2: The metal mesh layer formed on the transparent substrate was spin-coated at 2500 rpm to prepare a hybrid transparent electrode having a silver nanowire layer.

≪ Example 2 >

Step 1: Organic silver compounds were spin-coated on a transparent substrate at 2000 rpm and heat-treated at a temperature of 100 ° C for 60 seconds to form fine nanoparticles.

The material was irradiated with a power of 0.2 W through a laser direct patterning (LDP) method,

A metal mesh layer having a fine line width of 5 to 6 μm, a thickness of 200 nm and a pitch of 1500 μm.

Step 2: The metal mesh layer formed on the transparent substrate was spin-coated at 2500 rpm to prepare a hybrid transparent electrode having a silver nanowire layer.

≪ Example 3 >

A hybrid transparent electrode was fabricated in the same manner as in Example 2 except that laser patterning was performed so that the pitch was 1200 μm in the step 1 of Example 2. [

<Example 4>

A hybrid transparent electrode was prepared in the same manner as in Example 2 except that laser patterning was carried out so that the pitch was 900 μm in the step 1 of Example 2. [

&Lt; Example 5 >

A hybrid transparent electrode was fabricated in the same manner as in Example 2 except that laser patterning was performed so that the pitch was 600 μm in the step 1 of Example 2. [

&Lt; Example 6 >

A hybrid transparent electrode was prepared in the same manner as in Example 2 except that laser patterning was carried out so that the pitch was 300 μm in the step 1 of Example 2. [

&Lt; Example 7 >

Step 1: Silver nanowires were spin coated on a 1 inch size transparent substrate at 2500 rpm to form a silver nanowire layer.

Step 2: Organic silver compound was spin-coated on the silver nanowire layer formed on the transparent substrate at 4000 rpm and heat-treated at a temperature of 100 ° C for 60 seconds to form fine nanoparticles.

The material was irradiated with a power of 0.2 W through a laser direct patterning (LDP) method to produce a hybrid transparent electrode having a metal mesh layer having a fine line width of 3 to 6 μm and a pitch of 300 μm.

&Lt; Comparative Example 1 &

Silver nanowires were spin coated on a 1 inch size transparent substrate at 2500 rpm to form a silver nanowire layer.

&Lt; Comparative Example 2 &

Organic silver compounds were spin-coated on a transparent substrate at 4000 rpm and heat-treated at a temperature of 100 ° C for 60 seconds to form fine nanoparticles.

The material was irradiated at a power of 0.2 W through a laser direct patterning (LDP) method to form a metal mesh layer having a fine line width of 3 to 6 μm and a pitch of 300 μm.

&Lt; Comparative Example 3 &

Organic silver compounds were spin-coated on a transparent substrate at 2000 rpm and heat-treated at a temperature of 100 캜 for 60 seconds to form fine nanoparticles.

The material was irradiated with a power of 0.2 W through a laser direct patterning (LDP) method,

A metal mesh layer having a fine line width of 5 to 6 μm, a thickness of 200 nm and a pitch of 1500 μm.

&Lt; Comparative Example 4 &

A metal mesh layer was formed in the same manner as in Comparative Example 3, except that the laser patterning was performed so that the pitch of Comparative Example 3 was 1200 μm.

&Lt; Comparative Example 5 &

A metal mesh layer was formed in the same manner as in Comparative Example 3, except that the laser patterning was performed so that the pitch of Comparative Example 3 was 1200 μm.

&Lt; Comparative Example 6 >

A metal mesh layer was formed in the same manner as in Comparative Example 3, except that the laser patterning was performed so that the pitch of Comparative Example 3 was 600 μm.

&Lt; Comparative Example 7 &

A metal mesh layer was formed in the same manner as in Comparative Example 3, except that the laser patterning was carried out so that the pitch of Comparative Example 3 was 300 μm.

Metal mesh layer formation Silver wire layer formation Spin coating (rpm) Line width (탆) Pitch (占 퐉) Spin coating (rpm) Example 1 4000 3-6 300 2500 Example 2 2000 5-6 1500 2500 Example 3 2000 5-6 1200 2500 Example 4 2000 5-6 900 2500 Example 5 2000 5-6 600 2500 Example 6 2000 5-6 300 2500 Example 7 4000 3-6 300 2500 (first done) Comparative Example 1 × 2500 Comparative Example 2 4000 3-6 300 × Comparative Example 3 2000 5-6 1500 × Comparative Example 4 2000 5-6 1200 × Comparative Example 5 2000 5-6 900 × Comparative Example 6 2000 5-6 600 × Comparative Example 7 2000 5-6 300 ×

<Analysis 1> Analysis of sheet resistance change according to pitch of metal mesh layer

A 1 inch size transparent substrate made of glass was spin-coated with an organic silver solution and then patterned using a laser direct patterning (LDP) method with a fine line width of 3 to 6 μm and a pitch of 300, 600, 900 , 1200, 1500, and 1800 탆, respectively. The theoretical sheet resistance and transmittance of the transparent electrode are calculated by the following equations (1) and (2), and the results are shown in FIG.

&Quot; (1) &quot;

&Quot; (2) &quot;

Where ξ is a correction factor, t _G is the thickness of the metal wire, ρ _G is the resistivity, f _F is the filling factor, and the peeling factor is

Filling factor (f _F ) = W / (G + W)

Here, W represents the line width of the metal line forming the metal mesh layer, and G represents the metal line interval of the metal mesh layer.

As shown in FIG. 3, the transmittance gradually increases from 96.7% to 99.44% as the pitch of the metal lines forming the metal mesh becomes wider from 300 μm to 1800 μm. In addition, the theoretical sheet resistance value of the metal mesh is also markedly increased from 17.1 Ω / □ to 102.6 Ω / □. As the sheet resistance value increases, the electric conductivity decreases inversely. Therefore, it can be seen that as the pitch, which is the interval between the metal wires, increases, the conductivity increases but the electrical conductivity decreases.

<Analysis 2> Analysis of the change of permeability according to line width of metal mesh

A 1 inch size transparent substrate made of glass was spin-coated with an organic silver solution and then patterned using a laser direct patterning (LDP) method with a fine line width of 5 to 6 μm and a pitch of 300, 600, 900 , 1200, and 1500 .mu.m, respectively, and metal meshes having pitches of 300, 600, 900, 1200, and 1500 .mu.m, respectively, were formed with fine line widths of 3 - 4 .mu.m. The transmittance of the transparent electrode according to the wavelength was measured, and the results are shown in FIGS. 5 and 6. FIG.

6 and 7, it can be seen that the transmittance is improved as the pitch increases, and that the transmittance tends to increase as the wavelength increases.

FIG. 6 shows the transmittance measured from a metal mesh having a line width of 5 - 6 μm. FIG. 7 shows a transmittance measured from a metal mesh having a line width of 3 - 4 μm. When the line width is 3 - 4 μm It can be seen that the pitch increases about 1% as a whole as compared with the case where the line width is 5 - 6 탆. As a result, it can be seen that the transmittance increases when the line width of the metal line forming the metal mesh decreases.

<Analysis 3> analyzes the change of the transmittance according to the rotation speed of the nanowire

Each transparent substrate was prepared by spinning on a 1 inch size transparent substrate made of glass at 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, and 2500 rpm by spin coating to form a silver nanowire layer. At this time, the theoretical sheet resistances of the transparent substrate are 40, 120, 210, 390 and 480? / ?, respectively. The transmittance according to the wavelength of the transparent substrate was measured using a UV-Visible spectrophotometer. The results are shown in FIG.

Referring to FIG. 8, it can be seen that as the rotational speed increases, the sheet resistance increases and the sheet resistance of the transparent electrode increases as the silver nanowire layer is produced. This is because the electrical conductivity of the silver nano wire layer is increased but the transmittance is lowered depending on the rotation speed when the silver nanowire layer is formed so that the thickness of the silver nanowire layer affects the sheet resistance and transmittance .

Accordingly, it can be understood that the transparent electrode can be manufactured by appropriately selecting the transmittance and the electric conductivity by adjusting the formation conditions of the silver nanowire layer.

<Experimental Example 1> Scanning electron microscopic observation

In order to confirm the surface structure of the hybrid transparent electrode of the present invention, the surface of the transparent electrode prepared in Example 1 and Comparative Example 1 of the present invention was observed through a scanning electron microscope and the results are shown in FIG.

10, it can be seen that only a metal mesh having a thickness of 200 nm was formed on the surface of the transparent electrode prepared in Comparative Example 1 (left). On the surface of the transparent electrode prepared in Example 1 (right) It can be seen that the metal mesh of 200 nm and the nanowire are formed together.

<Experimental Example 2> Transmittance and sheet resistance of transparent electrode

To examine the transmittance and sheet resistance of the transparent electrode prepared in Example 2 of the present invention and Comparative Examples 1 and 3, the transmittance and the sheet resistance of each wavelength were measured using an ultraviolet-visible spectrophotometer, The results are shown in Fig.

According to FIG. 11, in the case of Comparative Example 1 in which the silver nanowire layer alone was formed, the sheet resistance was 97.2% at a wavelength of 550 nm and the sheet resistance was 480 Ω / □. In Comparative Example 3 in which the metal mesh layer alone was formed Has a transmittance of 98% at a wavelength of 550 nm and has a sheet resistance of 180 Ω / □.

On the other hand, in the case of Example 2 in which both the metal mesh layer and the silver nanowire layer were formed, the transmittance was 95% and the sheet resistance was 90 Ω / □ while the transmittance was lower than that of Comparative Example 1 and Comparative Example 3 It was found to have a lower sheet resistance than that of Comparative Examples 1 and 3.

As a result, it can be seen that the transparent electrode prepared in Example 2 has a similar low permeability to that of the metal mesh layer or the silver nanowire layer, but has a low sheet resistance value, thereby improving the electrical characteristics.

<Experimental Example 3> Sheet resistance analysis of transparent electrode

In order to examine the sheet resistance of the transparent electrodes prepared in Examples 2 to 6 and Comparative Examples 3 to 7 of the present invention, the sheet resistance was measured using an ultraviolet visible spectrophotometer, 12 and Table 2, respectively.

Sheet resistance (Ω / □) Example 2 (pitch: 1500 占 퐉) 90 Example 3 (Pitch 1200 占 퐉) 75 Example 4 (pitch: 900 占 퐉) 60 Example 5 (pitch: 600 占 퐉) 40 Example 6 (pitch 300 占 퐉) 20 Comparative Example 3 (pitch 1500 占 퐉) 122.5 Comparative Example 4 (pitch 1200 占 퐉) 98 Comparative Example 5 (pitch: 900 占 퐉) 73.5 Comparative Example 6 (pitch: 600 占 퐉) 49 Comparative Example 7 (pitch 300 占 퐉) 24.5

According to Fig. 12 and Table 1, in Examples 2 to 6 and Comparative Examples 3 to 7, the sheet resistance tends to decrease as the size of the generated pitch becomes smaller.

The sheet resistance of the comparative example 3 made of the conventional metal mesh layer was 122.5? / ?. In the case of Example 2 in which silver nanowires were coated on the metal mesh layer, the sheet resistance was 90? /? And it was found that the same tendency was observed also in Examples 3 to 6 and Comparative Examples 3 to 7 in which the size of the pitch was reduced.

As a result, it can be seen that the sheet resistance is reduced and the electrical characteristics are improved in the case of the silver nanowire-coated hybrid type as compared with the conventional metal mesh layer.

Claims (12)

A hybrid transparent electrode characterized by comprising a metal mesh layer and a silver nanowire layer on a transparent substrate.
The method according to claim 1,
Wherein the width of the metal wire forming the metal mesh layer is 100 占 퐉 and the distance between the metal wires is 300 占 퐉 to 2000 占 퐉.
The method according to claim 1,
Wherein the metal mesh layer is made of gold, silver, copper, aluminum, titanium, chromium, iron, cobalt, nickel, zinc, tin, iridium, indium, tungsten, molybdenum, platinum, iridium, hafnium, niobium, tantalum, tungsten and magnesium Wherein at least one selected from the group consisting of silicon,
The method according to claim 1,
Wherein the thickness of the metal mesh layer is 200 nm to 500 nm.
Forming a metal mesh layer on the transparent substrate (step 1); And
Forming a silver nanowire layer on the metal mesh layer formed on the transparent substrate (step 2);
And a second electrode formed on the second electrode.
Forming a silver nanowire layer on the transparent substrate (step 1); And
Forming a metal mesh layer on the silver nanowire layer formed on the transparent substrate (step 2);
And a second electrode formed on the second electrode.
The method according to claim 5 or 6,
Wherein the width of the metal line forming the metal mesh layer is 100 占 퐉 and the interval between the metal lines is 300 占 퐉 to 2000 占 퐉.
The method according to claim 5 or 6,
Wherein the thickness of the metal mesh layer is 200 nm to 500 nm.
The method according to claim 5 or 6,
Wherein the metal mesh layer is formed through a patterning process using a laser.
The method according to claim 5 or 6,
The silver nanowire layer is formed by one of the methods selected from the group consisting of spin coating, spray coating, dip coating and roll-to-roll coating. Wherein the transparent electrode is formed of a transparent conductive material.
The method according to claim 5 or 6,
Wherein the silver nanowire layer is formed by spin coating at a rotation speed of 500 rpm to 4000 rpm.
An electronic device comprising the hybrid transparent electrode of claim 1.

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