CN102569432B - Transparent electrode material and preparation method thereof - Google Patents

Abstract

The invention provides a transparent electrode material and a preparation method thereof. The material comprises a substrate and a conductive layer attached to the substrate. The conductive layer contains graphene and metal, and the sheet resistance of the conductive layer is 0.001-1000Ω/sq The light transmittance of the conductive layer in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%. Because the transparent electrode of the present invention contains a composite structure of metal and graphene, it not only has excellent properties of high light transmittance and low resistance, but also because the addition of graphene strengthens the structural stability and bending resistance of the transparent electrode, thereby The electron transport channel is further increased, and finally the conductivity of the transparent electrode is improved. The transparent electrode material of the present invention is widely used in photoelectric devices, photodetectors and semiconductor light emitting, especially flexible devices such as flexible solar cells and flexible displays. The preparation method of the invention has a simple process and is easy to realize industrialized production.

Description

A kind of transparent electrode material and preparation method thereof

technical field

The invention relates to a transparent electrode material and a preparation method thereof.

Background technique

At present, optoelectronic devices such as solar cells, semiconductor detectors, electroluminescence and flat panel displays all require transparent electrodes with low resistance and high light transmission performance. On this basis, the new generation of flexible optoelectronic devices requires bending-resistant transparent conductive electrodes. Transparent conductive oxide films (TCOs), metal films, carbon nanotubes, and graphene are commonly used as transparent electrodes for the aforementioned devices. Among TCOs, ITO (tin-doped indium oxide), which is an indium oxide system, is widely used. However, ITO has many shortcomings. For example, compared with metals such as Ag and Ni, the high resistivity of ITO cannot meet the development requirements of the lower resistivity of the above-mentioned devices, and the lack of indium reserves makes ITO expensive. It is unstable and not resistant to bending, so it is hoped to develop alternative materials. The light transmittance of carbon nanotubes is better than that of ITO only in the infrared region. Under the current process conditions, graphene is not as conductive as Ag, Ni and other metals, but graphene has good flexibility. Metal films have good electrical conductivity and light transmission, but are not stable on flexible substrates.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings of existing transparent electrode materials such as low transmittance, high resistivity, lack of flexibility and resistance to bending, and provide a metal film with high transmittance, good conductivity and excellent flexibility A transparent electrode material composited with graphene and a preparation method thereof.

The present invention provides a transparent electrode material, the transparent electrode material comprises a substrate and a conductive layer attached to the substrate, the conductive layer contains graphene and metal, the sheet resistance of the conductive layer is 0.001-1000Ω/sq, The light transmittance of the conductive layer in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.

The present invention also provides a method for preparing the above-mentioned transparent electrode material. The method includes forming a conductive layer on the substrate, the conductive layer contains graphene and metal, the sheet resistance of the conductive layer is 0.001-1000Ω/sq, and the conductive layer The light transmittance in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.

Because the transparent electrode of the present invention contains a composite structure of metal and graphene, it not only has excellent properties of high light transmittance and low resistance, but also because the addition of graphene strengthens the structural stability and bending resistance of the transparent electrode, thereby The electron transmission channel is further increased, and finally the conductivity of the transparent electrode is improved (it is speculated that this is because the flexibility of the graphene film can improve the performance of the metal film on the substrate; The role of the electronic bridge further increases the conductivity of the metal film; while graphene has a high transmittance in the ultraviolet, visible light, and infrared light regions, and will not affect the light transmission of the metal film.

The transparent electrode material of the present invention is widely used in photoelectric devices, photodetectors and semiconductor light emitting, especially flexible devices such as flexible solar cells and flexible displays. The preparation method of the invention has a simple process and is easy to realize industrialized production.

Description of drawings

Figure 1 is a schematic diagram of a-type transparent electrode materials.

Fig. 2 is a schematic diagram of a b-type transparent electrode material.

Fig. 3 is a schematic diagram of another b-type transparent electrode material.

4-7 are the front view and left (right) view of the a-type or b-type transparent electrode material of the present invention.

Explanation of reference signs

1 is a substrate; 2 is a metal layer; 3 is a graphene layer; 4 is a conductive layer formed by a mixture of graphene and metal.

Detailed ways

The invention provides a transparent electrode material, which comprises a substrate and a conductive layer attached to the substrate, the conductive layer contains graphene and metal, the sheet resistance of the conductive layer is 0.001-1000Ω/sq, the conductive The light transmittance of the layer in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%; preferably, the sheet resistance of the conductive layer is 0.001-100Ω/sq, and the conductive layer The light transmittance of the layer in the visible light region is 80-98%, and the light transmittance in the infrared light region is 80-98%.

Moreover, the resistance of the transparent electrode material of the present invention decreases by less than 2% after being bent 1,000 times on the flexible substrate and bending to 90° each time.

In the transparent electrode material of the present invention, the conductive layer can be formed by a mixture layer of graphene and metal, at this time, the weight ratio of graphene and metal can be 1:0.01-10000, and the graphene and metal The number of layers of the mixture layer can be 1-20 layers, and the thickness of each layer of the mixture layer of graphene and metal can be 0.2-300nm; in order to obtain better light transmittance and flexibility, preferably, the The weight ratio of graphene and metal is preferably 1:0.1-1000, and the thickness of each graphene-metal mixture layer is preferably 0.2-100 nm.

Preferably, the conductive layer in the transparent electrode material of the present invention can also be alternately formed by graphene layers and metal layers, the thickness of the graphene layer can be 0.2-10nm, the number of layers of the graphene layer It can be 1-10 layers, the thickness of the metal layer can be 0.2-300nm, and the number of layers of the metal layer can be 1-10 layers. In order to obtain better light transmittance and flexibility, preferably, the thickness of the graphene layer is 0.2-3nm, and the number of layers of the graphene layer can be 1-2 layers; the thickness of the metal layer is 0.5-10nm, the number of layers of the metal layer can be 1-2 layers. It should be clarified that the above-mentioned thickness refers to the average thickness of the graphene layer and the metal layer respectively.

Preferably, the metal layer in the present invention is a patterned metal film, and the metal film is preferably selected from a continuous metal film composed of micro-nano metal rings, a discontinuous metal film composed of micro-nano metal rings, a metal film composed of A two-dimensional metal microgrid formed by regular hole arrangement, a two-dimensional metal microgrid formed by irregular hole arrangement, a metal film composed of continuous metal islands, a metal film composed of discontinuous metal islands, and a metal film composed of one-dimensional metal nm One of the metal films composed of wires. In order to obtain better conductivity, light transmission and flexibility, it is further preferred to be a two-dimensional metal microgrid formed by regular hole arrangement.

In the transparent electrode material of the present invention, the metal can be one or more selected from silver, copper, gold, aluminum, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, preferably for gold or silver.

The Graphene involved in the present invention can be various Graphenes conventionally used in this field, the present invention has no special requirement to the layer number of described Graphene, can be the mixture of monolayer Graphene and multilayer Graphene, described The multilayer graphene is generally multilayer graphene with 2-10 layers. In addition, the graphene is graphene composed entirely of carbon atoms or graphene doped with heteroatoms. Wherein, the heteroatoms in the graphene doped with heteroatoms may be selected from one or more of nitrogen, oxygen, sulfur, boron and phosphorus.

In the present invention, different substrates can be selected according to different requirements. In the transparent electrode material of the present invention, the substrate can have a light transmittance of 90-100% in the visible light region, preferably 92-98%. 1. The light transmittance in the infrared region is 90-100%, preferably one or more of 92-98% transparent polymer film, glass and quartz, and the transparent polymer film can be a polyvinyl alcohol film , one or more of polyimide film, polyester film, polyvinyl chloride film, polycarbonate film, polyurethane film and polyacrylate film.

The conductive layer on the transparent electrode material provided by the present invention has three types, one is a mixture layer formed by graphene and metal, the other is an alternating graphene layer first formed, and then a metal layer, and another is an alternate The metal layer is formed first, and then the graphene layer is formed, and the latter two can be divided into one category according to the preparation method.

Therefore, the present invention provides two corresponding preparation methods for different types of conductive layers.

The present invention provides a method for preparing a transparent electrode material in which the above-mentioned conductive layer is formed by a mixture of metal and graphene. The method includes forming a conductive layer on a substrate, and the conductive layer is formed by a mixture layer of graphene and metal. The square resistance of the conductive layer is 0.001-1000Ω/sq, the light transmittance of the conductive layer in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.

The present invention has no special requirements on the method for forming the conductive layer on the substrate, for example, it can be carried out according to the following steps: attach the dispersion liquid containing graphene and metal to the surface of the substrate, and place it at 60-200°C for 1-120 minutes Finally, it is further preferred to place it at 80-120°C for 20-40min, then at 140-160°C for 2-10min, and then repeat the following steps 0-19 times: attach the dispersion containing graphene and metal to the obtained The surface of the mixture layer of graphene and metal is placed at 60-200°C for 1-120 minutes to obtain a transparent electrode material with a conductive layer, more preferably placed at 80-120°C for 20-40min, and then placed in Place at 140-160°C for 2-10min. Wherein, whether to repeat the steps can be determined according to needs, and the number of times, through the above steps, 1-20 layers of conductive layers can be formed on the transparent substrate.

In the above preparation method, the concentration of graphene in the dispersion containing graphene and metal can be 0.001-10mg/mL, and the concentration of metal can be 0.01-100mg/mL; The concentration of graphene in the dispersion liquid with metal is preferably 0.01-1 mg/mL, and the concentration of metal is preferably 0.1-10 mg/mL.

Preferably, the amount of the dispersion liquid containing graphene and metal is such that the thickness of each layer of the mixture layer containing graphene and metal in the obtained transparent electrode material is 0.2-300 nm.

In the present invention, the transparent electrode material prepared by this method is called a-type transparent electrode material. As shown in Figure 1, wherein, 1 is substrate; 4 is the conductive layer that is formed by the mixture of graphene and metal, and Fig. 1 has only illustrated the transparent electrode material of two layers in an embodiment of the present invention, in the art A skilled person can determine that more conductive layers formed of a mixture of graphene and metal can be sequentially formed on top of the conductive layer formed of a mixture of graphene and metal.

In the above-mentioned preparation method, the method of attaching the dispersion liquid containing graphene and metal to the surface of the transparent substrate or the surface of the mixture layer of graphene and metal obtained is not particularly limited, for example, it can be selected from the spin coating method. , one or more of spray coating, blade coating and dipping, preferably spin coating.

According to the method of the present invention, the dispersion liquid of described graphene and metal can be provided in various forms, such as sol form, described dispersion liquid containing graphene and metal can be prepared with reference to prior art, the present invention has no special requirements, I won't repeat them here.

The present invention also provides a method for preparing the above-mentioned transparent electrode material in which the conductive layer is alternately formed by graphene layers and metal layers. The method includes alternately forming metal layers and graphene layers on the substrate to form a conductive layer on the substrate. The sheet resistance of the conductive layer is 0.001-1000Ω/sq, the light transmittance of the conductive layer in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.

In the present invention, the transparent electrode material in which the conductive layer is alternately formed by graphene layers and metal layers is called b-type transparent electrode material, which includes the transparent electrode material in which the graphene layer is first formed on the substrate and then the metal layer is formed, as shown in the figure 2, wherein, 1 is a substrate; 2 is a metal layer; 3 is a graphene layer; and the transparent electrode material that forms a graphene layer after first forming a metal layer on the substrate, as shown in Figure 3, wherein, 1 is Substrate; 2 is a metal layer; 3 is a graphene layer. Fig. 2 and Fig. 3 just illustrate the transparent electrode material of two layers in two kinds of embodiments of the present invention respectively, and those skilled in the art can confirm that more graphene layers or metal layers can be between metal layer and graphene layer formed sequentially.

According to the method of the present invention, preferably, the thickness of the metal layer can be 0.2-300nm, preferably 0.5-10nm, and the number of layers of the metal layer can be 1-10 layers, preferably 1-2 layers; The thickness of the graphene layer can be 0.2-10 nm, preferably 0.2-3 nm; the number of layers of the graphene layer can be 1-10 layers, preferably 1-2 layers.

In the above-mentioned preparation method, the method for forming the graphene layer is not particularly limited, and can be carried out with reference to the prior art, for example, it can be selected from spin coating method, spray coating method, scraping method, dipping method or pulling method, It is preferably a spin-coating method; there is no particular limitation on the method for forming the metal layer, for example, it can be selected from the template method, electrospinning method, embossing method, self-assembly method, etching method, deposition method, electromagnetic field guidance method , sputtering, sol-gel, spin-coating, spray-coating, electrospinning or blade-coating, preferably a template method.

Since the metal used in the preparation method of the present invention, the substrate, and the mixture layer of graphene and metal that constitute the conductive layer, the thickness and type of the graphene layer, etc. are all the same as those involved in the product, here No longer.

The present invention is further described below in conjunction with embodiment.

In the following examples, measure visible light transmittance and infrared light transmittance with ultraviolet/visible/near-infrared spectrophotometer (PerkinElmer Lambda950); ) to measure the sheet resistance; the film thickness is tested with a scanning probe microscope (DigitalInstruments Dimension 3100); the surface morphology and size (such as the average particle size, etc.) of the test material are tested with a SEM scanning electron microscope (Hitachi S-4800, Japan).

Preparation Example 1

Preparation of graphene oxide sol

To the concentrated sulfuric acid of 98% by weight, the concentration of 1500g is to add 5.0g of natural flaky graphite (particle diameter is 200 μm), 5.0g of sodium nitrate and 25.0g of potassium permanganate, and the resulting mixture is placed in an ice bath at 0°C. After stirring for 5 h under the same conditions (that is, the temperature of the mixture was kept at 0° C. by ice bath), then stirred at 30° C. for 10 h; The concentration of 6mL is the hydrogen peroxide of 30% by weight, after stirring for 1h, filter, then the obtained filter cake is centrifugally washed with hydrochloric acid of 10% by weight, then centrifugally washed with deionized water, and the colloidal product after washing is added to 40 mL of deionized water was ultrasonically dispersed at a power of 200 W to obtain a graphene oxide sol (the content of graphene oxide was 20% by weight, and the content of water was 80% by weight).

Example 1

This example is to illustrate the preparation method of the b-type transparent electrode material of the present invention.

(1) Preparation of porous anodized aluminum template: two-step anodic oxidation method (according to HidekiMasuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb structures of Anodic Alumina, SCIENCE, 268 (9) 1995) provided method) to prepare a porous anodized aluminum sheet, the aperture of the porous anodized aluminum sheet measured by a scanning electron microscope is 50nm, and the hole spacing is 150nm;

(2) Electron beam evaporation metal layer: use electron beam evaporation instrument (Edwars, AUTO 500) to step (1) on the anodic aluminum oxide sheet that step (1) obtains and evaporate one layer of metallic silver, thickness 3nm;

(3) Remove the alumina template: Place a quartz sheet (Jinzhou Huamei Quartz Electric Appliance Factory, 2cm×2cm in size, 1mm in thickness) under the anodized aluminum sheet that has been vapor-deposited with metallic silver in step (2), at a concentration of 1%. Dissolve the anodic aluminum oxide in the phosphoric acid solution, and the metal silver grid with holes will naturally settle on the quartz plate; wash the excess phosphoric acid and metal ions on the quartz plate with deionized water, and dry at 100°C for 4 hours;

(4) prepare graphene oxide thin film: the graphene oxide sol obtained in the thick preparation example 1 of one deck 6nm is spin-coated with spin coater with spin coater on the quartz sheet that metal grid is obtained in step (3), 100 Dry at ℃ for 10 minutes;

(5) Thermal reduction of graphene oxide: under the protection of Ar gas, the quartz sheet containing the graphene oxide film with a thickness of 0.8nm obtained in step (4) is put into a quartz tube, and then the quartz tube is put into a tube furnace , at a heating rate of 200°C per hour and slowly heated to 800°C for 10 minutes, then slowly cooled to room temperature in a furnace under the protection of Ar gas, and reduced to obtain a transparent electrode material containing graphene and metallic silver. The front view and left (right) view of the transparent electrode material are shown in A and B in Fig. 4.

The thickness of the metal layer of the transparent electrode material is 3 nm, and the number of metal layers is 1 layer; the thickness of the graphene layer is 0.8 nm, and the number of graphene layers is 1 layer.

The transparent electrode material has a light transmittance of 92% in the visible light region, a light transmittance of 92% in the infrared light region, and a sheet resistance of 5Ω/sq.

Example 2

This example is to illustrate the preparation method of the b-type transparent electrode material of the present invention.

(1) The method for chemical vapor deposition prepares nitrogen-doped graphene: with coating machine (KYUY Zhongkekeyi Technology Development Co., Ltd., model SBC-2), with Ni as the target material, deposition time 20s, on a quartz sheet ( Jinzhou Huamei Quartz Electric Appliance Factory, with a size of 2cm×2cm and a thickness of 1mm) was thermally evaporated with 50nm thick Ni. Put the quartz piece into the quartz tube, pass hydrogen (20sccm) and argon (100sccm), when the temperature of the center of the furnace rises to 800°C, feed 60sccm of CH4 and 60sccm of NH3, put the quartz tube into the furnace After 10 min, the sample was cooled to room temperature under hydrogen flow to obtain a nitrogen-doped graphene film. The Ni on the film was dissolved with a phosphoric acid solution with a concentration of 1%, and the graphene surface was washed three times with deionized water.

(2) Preparation of polystyrene microspheres: Add 10 mL of styrene and 150 mL of water into a 500 mL three-neck flask, ventilate with nitrogen for 15 min, stir in a constant temperature water bath at 70 °C for 20 min, add 0.2 g of potassium persulfate, and react at 70 °C for 24 h. A monodisperse aqueous solution of polystyrene microspheres was obtained by centrifugal separation (the concentration of styrene microspheres was 10% by weight, and the average particle diameter of the styrene microspheres was 1.3 μm).

(3) Preparation of patterned metal thin film with polystyrene microsphere monolayer film as template: add 0.05mL styrene and 5mL Dehydrated alcohol, then add 0.15 μ L of sulfuric acid (concentration is 98%) in this solution, ultrasonic 15 minutes, put the quartz sheet that above-mentioned steps (1) process has the surface of graphene film at the bottom of the container, let go in the container liquid, washed three times with deionized water. Using a plasma etching (RIE) system (SENTECH, ETCHCAB200), etching with oxygen ions for 10 s, the particle size of polystyrene microspheres was reduced to 1 μm. Using a magnetron sputtering apparatus (ULVAC Inc, ACS-400-C4), at a working pressure of 0.5Pa and a power of 40W, sputtering perpendicular to the quartz plate for 10s, depositing metal Al in the voids of polystyrene microspheres to obtain 3nm Thick Al, pore spacing 600nm, pore diameter 1μm. The aforementioned quartz plate deposited with metal was immersed in toluene solution to dissolve template polystyrene microspheres, and washed with deionized water to obtain a transparent electrode material containing metal aluminum and N-doped graphene. The front view and left (right) view of the transparent electrode material are shown in A and B in Fig. 5.

The thickness of the metal layer of the transparent electrode material is 3 nm, and the number of metal layers is 1 layer; the thickness of graphene is 1.2 nm, and the number of graphene layers is 1 layer.

The visible light transmittance of the transparent electrode material is 98%, the infrared light transmittance is 98%, and the sheet resistance is 3Ω/sq.

Example 3

This example is to illustrate the preparation method of the b-type transparent electrode material of the present invention.

(1) Preparation of graphene sol: dissolve 600mg sodium borohydride in 15g water, add the sodium borohydride solution obtained in the graphene oxide sol obtained in 50mL Preparation Example 1, adjust the pH value of the solution with 5% by weight of sodium carbonate solution To 9, these mixtures were stirred at 80°C for 1 h, then centrifuged and washed 5 times with deionized water at a speed of 5000 rpm, and the washed graphene was dissolved in a 1:1 mixed solution of water and ethanol to obtain a concentration of 10mg/mL graphene sol.

(2) Preparation of graphene film: adopt dipping and pulling method, immerse polyethylene terephthalate film PET (Japan AICA, model HC2106, size is 2cm * 2cm, thickness 0.188mm) into step (1 ) in the graphene sol obtained, then the PET is pulled out of the liquid surface at a uniform speed in the direction perpendicular to the horizontal plane, the excess graphene sol on the back of the PET is washed with deionized water, and dried at room temperature to obtain a graphene layer with a thickness of 7nm .

(3) Preparation of photoresist template by ultraviolet lithography: using the method of ultraviolet lithography, first spin-coat 5mL photoresist (company ALLRESIST, model AR-N4340) with a spin coater on the graphene layer obtained in step (2) , and then placed a template with a vertical nanowire grid pattern (purchased from the Institute of Semiconductors, Chinese Academy of Sciences) on the photoresist in the darkroom for ultraviolet exposure, and the photoresist was patterned under the action of a developer (ALLRESIST manufacturer, model AR300-26) The template nanowire grid pattern is obtained by etching. Detected under a scanning electron microscope, the photoresist nanowires have a width of 2 μm and a line spacing of 20 μm.

(4) Evaporate Cu in the photoresist gap: use a thermal evaporation method to vapor-deposit Cu target on the above-mentioned PET sheet for 10 s, and obtain 3 nm thick Cu in the photoresist gap. The photoresist was dissolved and washed off with a developer, and then washed three times with deionized water to obtain a transparent electrode material containing metal Cu and graphene.

(5) Repeat the aforementioned steps (1) and (2) for the transparent electrode material obtained in step (4), and prepare a layer of graphene film on the Cu transparent film to obtain the transparent electrode material of double-layer graphene. The front view and left (right) view of the transparent electrode material are shown in A and B in Fig. 6.

The thickness of the metal layer of the transparent electrode material is 3nm, and the number of metal layers is 1; the thickness of graphene is 1.2nm; and the number of graphene layers is 2 layers.

The visible light transmittance of the transparent electrode material is 70%, the infrared light transmittance is 70%, and the sheet resistance is 0.001Ω/sq. After the above-mentioned transparent electrode material is bent 1000 times to 90° each time, the visible light transmittance is 70%, the infrared light transmittance is 70%, and the sheet resistance is 0.001Ω/sq.

Example 4

This example is to illustrate the preparation method of the a-type transparent electrode material of the present invention.

(1) Preparation of graphene sol: Consistent with step (1) of Example 3, the graphene sol with a concentration of 10 mg/mL was obtained, diluted with deionized water to obtain 0.1 mg/mL graphene sol.

(2) Preparation of Ag nanowire and graphene mixed sol: monodisperse Ag nanowire (according to the literature Yi Cui et al. Scalable Coating and Properties of Transparent, Flexible, SilverNanowire Electrodes, ACS NANO, 2010, 4(5): 2955- Prepared by the method in 2963, the particle size is 40nm-100nm, 2mg/mL) is mixed with the 0.1mg/mL graphene sol obtained in step (1), and the volume mixing ratio is 1:1. Ultrasound for 30 minutes (ultrasonic power 20kW);

(3) Preparation of mixed films of Ag nanowires and graphene: Scrape 1mL of mixed sol onto PET (AICA, model HC2106, size 2cm×2cm, thickness 0.188mm) with a glass rod by scrape coating and dried to obtain a transparent electrode material. The front view and left (right) view of the transparent electrode material are shown in A and B in Fig. 7.

The thickness of the metal Ag and graphene mixed layer of the transparent electrode material is 3 nm, and the number of metal and graphene mixed layers is 1 layer.

The visible light transmittance of the transparent electrode material is 92%, the infrared light transmittance is 92%, and the sheet resistance is 100Ω/sq. After the above transparent electrode material is bent 1000 times to 90° each time, the visible light transmittance is 92%, the infrared light transmittance is 92%, and the sheet resistance increase is less than 5%.

Claims (10)

1. a transparent electrode material, it is characterized in that, this material comprises substrate and is attached to this on-chip conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region

Wherein, described conductive layer is formed by the mixture layer of Graphene and metal, the weight ratio of described Graphene and metal is 1:0.01-10000, and the number of plies of the mixture layer of described Graphene and metal is 1-20 layer, and the thickness of the mixture layer of Graphene and metal is 0.2-300nm described in every one deck; Or

Described conductive layer is alternately formed by graphene layer and metal level, and the thickness of described graphene layer is 0.2-10nm, and the number of plies of described graphene layer is 1-10 layer, the thickness of described metal level is 0.2-300nm, the number of plies of described metal level is 1-10 layer, wherein, and the metal film that described metal level is patterning.

2. transparent electrode material according to claim 1, wherein, described metal is to be selected from one or more in silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium.

3. transparent electrode material according to claim 1, wherein, described substrate be 90-100% at the light transmittance of visible region, one or more in be 90-100% at the light transmittance of infrared light region glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and polyacrylate film.

4. the preparation method by the transparent electrode material described in any one in claim 1-3, it is characterized in that, the method comprises, on substrate, form conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, and described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region.

5. method according to claim 4, wherein, the described method that forms conductive layer on substrate comprises, the dispersion liquid that contains Graphene and metal is attached to substrate surface, at 60-200 DEG C, place after 1-120 minute, then repeat following steps 0-19 time: the dispersion liquid that contains Graphene and metal is attached to the surface of the mixture layer of obtained Graphene and metal, at 60-200 DEG C, places 1-120 minute.

6. method according to claim 5, wherein, described in contain Graphene and metal dispersion liquid in the concentration of Graphene be 0.001-10mg/mL, the concentration of metal is 0.01-100mg/mL.

7. according to the method described in any one in claim 5-6, wherein, the consumption of the dispersion liquid that every one deck contains Graphene and metal is that the thickness of the mixture layer that contains Graphene and metal described in every one deck in the transparent electrode material that makes to obtain is 0.2-300nm.

8. method according to claim 4, wherein, the described method that forms conductive layer on substrate comprises, alternately forms metal level and graphene layer on substrate.

9. method according to claim 8, wherein, the thickness of described metal level is 0.2-300nm, and the number of plies of described metal level is 1-10 layer, and the thickness of described graphene layer is 0.2-10nm, and the number of plies of described graphene layer is 1-10 layer.

10. according to the method described in any one in claim 5-6,8 and 9, wherein, described metal is to be selected from one or more in silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, and described substrate is is 90-100% at the light transmittance of visible region, one or more in be 90-100% at the light transmittance of infrared light region glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and polyacrylate film.