WO2012079360A1 - Transparent electrode material and manufacturing method thereof - Google Patents

Transparent electrode material and manufacturing method thereof Download PDF

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Publication number
WO2012079360A1
WO2012079360A1 PCT/CN2011/076367 CN2011076367W WO2012079360A1 WO 2012079360 A1 WO2012079360 A1 WO 2012079360A1 CN 2011076367 W CN2011076367 W CN 2011076367W WO 2012079360 A1 WO2012079360 A1 WO 2012079360A1
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Prior art keywords
graphene
metal
layer
transparent electrode
electrode material
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PCT/CN2011/076367
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French (fr)
Chinese (zh)
Inventor
智林杰
邱腾飞
梁明会
王杰
罗彬�
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国家纳米科学中心
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Publication of WO2012079360A1 publication Critical patent/WO2012079360A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor
    • H01L33/42—Transparent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a transparent electrode material and a preparation method thereof. Background technique
  • TCOs Transparent conductive oxide thin films
  • metal films metal films
  • carbon nanotubes and graphene are commonly used as transparent electrodes for the above devices.
  • ITO indium oxide based ITO (tin-doped indium oxide) is widely used in TCOs.
  • ITO has many shortcomings, for example: Compared with metals such as Ag and Ni, the higher resistivity of ITO cannot meet the development requirements of the lower resistivity of the above devices, and the lack of indium reserves makes the cost of germanium expensive, and ITO is on a flexible substrate. It is unstable and not resistant to bending, so it is hoped to develop alternative materials.
  • the transmittance of carbon nanotubes is superior to ITO only in the infrared region. Under current process conditions, graphene is not as conductive as Ag, Ni, etc., but graphene has good flexibility.
  • the metal film is excellent in conductivity and light transmittance, but is unstable on a flexible substrate. Summary of the invention
  • the object of the present invention is to overcome the shortcomings of the prior transparent electrode materials such as low transmittance, high resistivity, lack of flexibility and resistance to flexing, and a metal film having high transmittance, good electrical conductivity and excellent flexibility.
  • the present invention provides a transparent electrode material, the transparent electrode material comprising a substrate and a conductive layer attached to the substrate, the conductive layer containing graphene and a metal, and the sheet resistance of the conductive layer is ⁇ /sq or less.
  • 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 transparent electrode material, the method comprising: forming a conductive layer on a substrate, the conductive layer containing graphene and a metal, the conductive layer having a sheet resistance of ⁇ /sq or less, the conductive layer being The light transmittance in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.
  • 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 electrical resistance, but also because the addition of graphene enhances structural stability and bending resistance of the transparent electrode, Further increasing the electron transport channel, ultimately improving the conductivity of the transparent electrode (presumably because of graphene).
  • the flexibility of the film can improve the performance of the metal film on the substrate; the conductivity of the graphene can act as an electron bridge after compounding with the metal film to further increase the conductivity of the metal film; and the graphene is in the ultraviolet, visible, The transmittance of the infrared light region is high, and does not affect the light transmittance of the metal film).
  • the transparent electrode material of the present invention is widely used in photovoltaic devices, photodetectors, and semiconductor light-emitting devices, particularly flexible devices such as flexible solar cells and flexible displays.
  • the preparation method of the invention is simple in process and easy to realize industrial production.
  • Figure 1 is a schematic illustration of a type a transparent electrode material.
  • Figure 2 is a schematic illustration of a b-type transparent electrode material.
  • Figure 3 is a schematic illustration of another b-type transparent electrode material.
  • 1 is a substrate; 2 is a metal layer; 3 is a graphene layer; and 4 is a conductive layer formed of a mixture of graphene and a metal.
  • the present invention provides a transparent electrode material comprising a substrate and a conductive layer attached to the substrate, the conductive layer containing graphene and a metal, the conductive layer having a sheet resistance of ⁇ /sq or less, 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%; preferably, the conductive layer has a sheet resistance of ⁇ /sq or less, the conductive layer
  • the light transmittance in the visible light region is 80-98%, and the light transmittance in the infrared light region is 80-98%.
  • the conductive layer containing graphene and metal may be implemented in various forms, for example, may be formed of a mixture layer of graphene and metal, or may be composed of a graphene layer and a metal layer. Alternatively, it may be formed by alternately forming a mixture layer of graphene and metal with a graphene layer or a metal layer, preferably formed of a mixture layer of graphene and metal or alternately formed of a graphene layer and a metal layer.
  • the weight ratio of the graphene to the metal may be 1:0.01-10000, the graphene and the metal
  • the layer of the mixture layer may be 1-20 layers, each layer of the mixture of graphene and metal may have a thickness of 0.2-300 nm;
  • the weight ratio of the graphene to the metal is preferably 1:0.1 to 1000, and the thickness of the layer of the mixture of the graphene and the metal in each layer is preferably 0.2. -100nm.
  • the layer of the mixture of graphene and metal refers to a layer formed of a mixture of graphene and metal.
  • the thickness of the graphene layer may be 0.2-10 nm, and the number of layers of the graphene layer It may be 1-10 layers, the metal layer may have a thickness of 0.2-300 nm, and the metal layer may have a layer number of 1-10 layers.
  • the thickness of the graphene layer is preferably 0.2-3 nm, and the number of layers of the graphene layer may be 1-2 layers; the thickness of the metal layer is The number of layers of the metal layer may be 1-2 layers from 0.5 to 100 nm. It is to be understood that the above thicknesses refer to the average thickness of the graphene layer and the metal layer, respectively.
  • Each of the conductive layers in the transparent electrode material of the present invention may be patterned or unpatterned.
  • the metal layer in the present invention is a patterned metal film
  • the metal film is preferably a continuous metal film selected from a micro-nano metal ring, a discontinuous metal film composed of a micro-nano metal ring, a two-dimensional metal microgrid formed by regular pore arrangement, a two-dimensional metal microgrid formed by irregular pore arrangements, a metal film composed of continuous metal islands, a metal film composed of discontinuous metal islands, and a one-dimensional metal nanometer One of the metal films composed of wires.
  • a two-dimensional metal microgrid formed by regular pore arrangement is further preferable.
  • the metal may be one or more selected from the group consisting of silver, copper, gold, aluminum, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, preferably It is gold or silver.
  • the graphene involved in the present invention may be various graphenes conventionally used in the art, and the present invention has no particular requirement on the number of layers of the graphene, and may be a mixture of a single layer of graphene and a plurality of graphenes.
  • the multilayer graphene is generally 2-10 layers of multilayer graphene, and the graphene is graphene composed entirely of carbon atoms or graphene doped with hetero atoms.
  • the hetero atom in the graphene doped with a hetero atom may be selected from one or more of nitrogen, oxygen, sulfur, boron, and phosphorus.
  • different substrates may be selected according to different needs, and may be a flexible substrate or a non-flexible substrate.
  • the substrate may be in visible light.
  • the light transmittance of the region is 90-100%, preferably 92-98%, and the light transmittance in the infrared light region is 90-100%, preferably 92-98%, one of transparent polymer film, glass and quartz.
  • the transparent polymer film may be a polyvinyl alcohol film, a polyimide film, a polyethylene terephthalate film, a polyvinyl chloride film, a polycarbonate film, a polyurethane film, and a polyacrylate.
  • One or more of the membranes may be a polyvinyl alcohol film, a polyimide film, a polyethylene terephthalate film, a polyvinyl chloride film, a polycarbonate film, a polyurethane film, and a polyacrylate.
  • the conductive layer provided on the transparent electrode material of the present invention has three types, one is graphene. a mixture layer formed of a metal, the other is an alternating first graphene layer, and then a metal layer, and an alternate first metal layer is formed, and then a graphene layer is formed, and the latter two can be divided according to a preparation method. For a class.
  • the present invention provides two corresponding methods of preparation for different types of conductive layers.
  • the present invention provides a method for preparing a transparent electrode material in which the above conductive layer is formed of a mixture layer of metal and graphene, the method comprising: forming a conductive layer on a substrate, the conductive layer being formed of a mixture layer of graphene and a metal, forming The sheet resistance of the conductive layer is ⁇ /sq or less, and 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 requirement for the method of forming a conductive layer on a substrate, for example, the following steps can be performed: attaching a dispersion containing graphene and a metal to the surface of the substrate, and placing it at 60-200 ° C for l-120 min. Thereafter, cooling to room temperature (10-40 ° C), and then repeating the steps of 0-19 times: attaching a dispersion containing graphene and a metal to the surface of the obtained layer of the mixture of graphene and metal, at 60- After standing at 200 ° C for l-120 min, it was cooled to room temperature (10-40 ° C): A transparent electrode material with a conductive layer was obtained. Wherein, the steps may be repeated to determine whether or not to proceed, and the number of times of the process. Through the above steps, a conductive layer of 1-20 layers may be formed on the transparent substrate.
  • the concentration of graphene in the dispersion containing graphene and metal may be 0.001 to 10 mg/mL, and the concentration of metal may be 0.01 to 100 mg/mL; for convenience of operation, the graphene is contained.
  • the concentration of graphene in the dispersion with the metal is preferably 0.01-1 mg/mL, and the concentration of the metal is preferably 0.1-10 mg/mL.
  • the present invention has no particular requirement for the dispersion medium in the dispersion, and can be carried out by referring to the prior art.
  • it can be water and a common organic solvent used for preparing a dispersion containing graphene, and will not be described herein.
  • the dispersion liquid in the present invention may be in various forms as long as the metal and graphene are uniformly distributed in the dispersion, and may be, for example, a sol form, a solution form or the like.
  • the range of the size of the metal particles in the dispersion is wide, and those skilled in the art can easily select according to the technical solution described in the present invention, preferably on the order of micrometers and/or nanometers, more preferably nanometers. level.
  • the dispersion containing graphene and metal is used in an amount such that the layer containing the mixture of graphene and metal in each of the obtained transparent electrode materials has a thickness of 0.2 to 300 nm.
  • the transparent electrode material prepared by this method is referred to as an a-type transparent electrode material.
  • a-type transparent electrode material As shown in FIG. 1, wherein 1 is a substrate; 4 is a conductive layer formed of a mixture of graphene and metal, and FIG. 1 only illustrates a two-layer transparent electrode material in an embodiment of the present invention, The skilled person can determine that more conductive layers formed from a mixture of graphene and metal can be formed sequentially over the conductive layer formed from a mixture of graphene and metal.
  • a method of attaching a dispersion containing graphene and a metal to the surface of a transparent substrate or adhering to the surface of the obtained mixture layer of graphene and metal is not particularly limited, and for example, may be selected from a spin coating method.
  • a spin coating method One or more of a spray coating method, a knife coating method, and a dipping method, preferably a spin coating method.
  • the dispersion of graphene and metal may be provided in various forms, such as a sol form, and the dispersion containing graphene and metal may be prepared according to the prior art, and the present invention has no special requirements. I will not repeat them here.
  • the present invention also provides a method for preparing a transparent electrode material in which the conductive layer is alternately formed of a graphene layer and a metal layer, the method comprising: alternately forming a metal layer and a graphene layer on the substrate to form a conductive layer on the substrate,
  • the sheet resistance of the conductive layer is ⁇ /sq or less, 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 transparent electrode material in which the conductive layer is alternately formed of the graphene layer and the metal layer is referred to as a b-type transparent electrode material, and includes a transparent electrode material which forms a metal layer after forming a graphene layer on the substrate, as shown in the figure. 2, wherein 1 is a substrate; 2 is a metal layer; 3 is a graphene layer; and a transparent electrode material forming a graphene layer after forming a metal layer on the substrate, as shown in FIG. 3, wherein 1 is The substrate; 2 is a metal layer; 3 is a graphene layer. 2 and 3 are only two layers of transparent electrode materials in two embodiments of the present invention, respectively, and those skilled in the art can determine that more graphene layers or metal layers can be in the metal layer and the graphene layer. It is formed in order.
  • the metal layer may have a thickness of 0.2-300 nm, preferably 0.5-100 nm, and the metal layer may have a layer number of 1-10 layers, preferably 1-2 layers;
  • the thickness of the graphene layer may be from 0.2 to 10 nm, preferably from 0.2 to 3 nm; the number of layers of the graphene layer may be from 1 to 10 layers, preferably from 1 to 2 layers.
  • the method for forming the graphene layer is not particularly limited and may be carried out by referring to the prior art, and may be, for example, selected from a spin coating method, a spray coating method, a knife coating method, a dipping method or a pulling method.
  • the method of forming the metal layer is not particularly limited, and may be, for example, selected from the group consisting of a stencil method, an electrospinning method, an imprint method, a self-assembly method, an etching method, a deposition method, and an electromagnetic field guiding method.
  • the sputtering method, the sol-gel method, the spin coating method, the spray coating method, the electrospinning or the doctor blade method are preferably a template method.
  • the metal, the substrate, and the mixture of the graphene and the metal constituting the conductive layer, the thickness and the kind of the graphene layer, etc., which are used in the production method of the present invention are the same as those involved in the product, No longer.
  • the visible light transmittance and the infrared light transmittance were measured by an ultraviolet/visible/near infrared spectrophotometer (PerkinElmer Lambda 950); the four-probe tester with a double electric test (Guangzhou four-probe technology RTS- 9) Determine the sheet resistance; the film thickness is tested with a scanning probe microscope (Digital Instruments Dimension 3100); SEM scanning electron microscopy (Hitachi, Hitachi S-4800, Japan) was used to test the surface morphology and size (such as average particle size) of the material.
  • an ultraviolet/visible/near infrared spectrophotometer PerkinElmer Lambda 950
  • the four-probe tester with a double electric test (Guangzhou four-probe technology RTS- 9) Determine the sheet resistance
  • the film thickness is tested with a scanning probe microscope (Digital Instruments Dimension 3100); SEM scanning electron microscopy (Hitachi, Hitachi S-4800, Japan) was used to test the surface morphology and size (such as average particle
  • This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
  • Electron beam evaporation metal layer an electron beam evaporator (Edwars, AUTO 500) is used to vaporize a layer of metallic silver on the anodized aluminum sheet obtained in step (1) to a thickness of 3 nm;
  • step (3) Removal of the alumina template: Place the quartz plate under the anodized aluminum sheet with metal silver vapor deposited in step (2) (Jinzhou Huamei Quartz Electric Factory, size 2 C mx2cm, thickness lmm) at a concentration of 1%
  • the anodized aluminum is dissolved in the phosphoric acid solution, and the porous metal silver mesh is naturally deposited on the quartz plate; the excess phosphoric acid and metal ions on the quartz plate are washed with deionized water, and dried at 100 ° C for 4 h;
  • step (4) Thermal reduction of graphene oxide: under Ar gas protection, the thickness of step (4) is 0.8 nm
  • the quartz sheet of the graphene oxide film is placed in a quartz tube, and then the quartz tube is placed in a tube furnace, and the temperature is slowly raised to 800 ° C per hour at a heating rate of 10 ° C for 10 min, and then in the furnace under the protection of Ar gas.
  • the mixture was slowly cooled to room temperature, 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 as A and B in FIG.
  • the thickness of the metal layer of the transparent electrode material is 3 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene layer is 0.8 nm, and the number of layers of the graphene layer 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 5 Q/sq.
  • This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
  • the sample After entering the center of the furnace, after lOmin, the sample was cooled to room temperature under a hydrogen stream to obtain a nitrogen-doped graphene film, and the Ni on the film was dissolved in a phosphoric acid solution having a concentration of 1%, and the surface of the graphene was washed three times with deionized water.
  • RIE plasma etching
  • the metal plated quartz plate is immersed in a toluene solution to dissolve the template polystyrene microspheres, and washed with deionized water to obtain a metal containing aluminum and lanthanum doped stone.
  • the thickness of the metal layer of the transparent electrode material is 3 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene is 1.2 nm, and the number of layers of the graphene layer is 1 layer.
  • the transparent electrode material has a visible light transmittance of 98%, an infrared light transmittance of 98%, and a sheet resistance of 3Q/sq.
  • This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
  • the thickness of the metal layer of the transparent electrode material was 3 nm, the number of layers of the metal layer was 1 layer; the thickness of the graphene was 1.2 nm; and the number of layers of the graphene was 2 layers.
  • the transparent electrode material has a visible light transmittance of 70%, an infrared light transmittance of 70%, and a sheet resistance of 0.001 Q/sq.
  • This embodiment is a method for preparing a type a transparent electrode material of the present invention.
  • the thickness of the mixed layer of metal Ag and graphene of the transparent electrode material is 3 nm, and the number of layers of the mixed layer of metal and graphene is
  • the transparent electrode material had a visible light transmittance of 92%, an infrared light transmittance of 92%, and a sheet resistance of 100 Q/sq.
  • This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
  • Electron beam evaporation metal layer an electron beam evaporator (Edwars, AUTO 500) is used to vaporize a layer of metallic silver on the anodized aluminum sheet obtained in the step (1) to a thickness of 20 nm;
  • step (3) Removal of the alumina template: Place the quartz plate under the anodized aluminum sheet with metal silver vapor deposited in step (2) (Jinzhou Huamei Quartz Electric Factory, size 2 C mx2cm, thickness lmm) at a concentration of 1%
  • the anodized aluminum is dissolved in the phosphoric acid solution, and the porous metal silver mesh is naturally deposited on the quartz plate; the excess phosphoric acid and metal ions on the quartz plate are washed with deionized water, and dried at 100 ° C for 4 h;
  • the thickness of the metal layer of the transparent electrode material is 20 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene layer is 0.8 nm, and the number of layers of the graphene layer is 1 layer.
  • the transparent electrode material has a light transmittance of 85% in the visible light region, a light transmittance of 85% in the infrared light region, and a sheet resistance lQ/sq.
  • This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
  • the quartz sheet into a quartz tube, through the hydrogen (of 20 sccm) and argon (lOOsccm), when the furnace temperature is raised to 800 ° C, into the 60sccm of 60sccm of CH 4 and NH 3, the quartz discharge tube
  • the sample After entering the center of the furnace, after lOmin, the sample was cooled to room temperature under a hydrogen stream to obtain a nitrogen-doped graphene film, and the Ni on the film was dissolved in a phosphoric acid solution having a concentration of 1%, and the surface of the graphene was washed three times with deionized water.
  • RIE plasma etching
  • the aforementioned metal-deposited quartz plate was immersed in a toluene solution to dissolve the template polystyrene microspheres, and washed with deionized water to obtain a transparent electrode material containing metal aluminum and cerium-doped graphene.
  • the thickness of the metal layer of the transparent electrode material is 10 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene is 1.2 nm, and the number of layers of the graphene layer is 1 layer.
  • the transparent electrode material has a visible light transmittance of 94%, an infrared light transmittance of 94%, and a sheet resistance of 2Q/sq.

Abstract

A transparent electrode material and a manufacturing method thereof are provided. The material comprises a substrate (1) and a conductive layer adhered to the substrate (1). The conductive layer comprises graphene and metal. The conductive layer has a sheet resistance of less than 1000Ω/sq, a light transmission of 70-98% in the visible region, and a light transmission of 70-98% in the infrared region. Because of having a composite structure including metal and graphene, the transparent electrode has excellent performances of high transmittance and low resistance. Adding graphene can enhance structural stability and bending resistance of the transparent electrode, further increase electron transport channels, and finally improve the electrical conductivity of the transparent electrode. The transparent electrode material is widely used in optoelectronic devices, photodetectors and semiconductor luminescence, especially in flexible devices such as flexible solar cells, flexible display devices. The manufacturing method is simple, and the industrial production is easily achieved.

Description

一种透明电极材料及其制备方法 技术领域  Transparent electrode material and preparation method thereof
本发明涉及一种透明电极材料及其制备方法。 背景技术  The invention relates to a transparent electrode material and a preparation method thereof. Background technique
目前， 太阳能电池、 半导体探测器、 电致发光及平板显示器等光电器件均需要低 电阻、 高透光性能的透明电极。 而新一代柔性光电器件在此基础上更需要耐弯曲的透明 导电电极。 透明导电氧化物薄膜 （TCOs), 金属膜， 碳纳米管以及石墨烯通常作为上述 器件的透明电极。 TCOs中作为氧化铟系的 ITO (掺锡氧化铟） 被广泛使用。 但是 ITO 存在许多不足， 例如： 相对 Ag、 Ni等金属而言， ITO的电阻率较高不能满足上述器件 更低电阻率的发展要求， 而且铟储量的匮乏使得 ΠΌ的造价昂贵， ITO在柔性基底上不 稳定， 不耐弯曲， 所以希望开发出其替代材料。 碳纳米管透光率仅在红外区优于 ITO。 目前工艺条件下， 石墨烯导电性不如 Ag、 Ni等金属， 但是石墨烯具有很好的柔性。 金 属膜导电性和透光性较好， 但是在柔性基片上不稳定。 发明内容  At present, photovoltaic devices such as solar cells, semiconductor detectors, electroluminescence, and flat panel displays require transparent electrodes with low resistance and high light transmission properties. On the basis of this, a new generation of flexible optoelectronic devices requires a transparent conductive electrode that is resistant to bending. Transparent conductive oxide thin films (TCOs), metal films, carbon nanotubes, and graphene are commonly used as transparent electrodes for the above devices. Indium oxide based ITO (tin-doped indium oxide) is widely used in TCOs. However, ITO has many shortcomings, for example: Compared with metals such as Ag and Ni, the higher resistivity of ITO cannot meet the development requirements of the lower resistivity of the above devices, and the lack of indium reserves makes the cost of germanium expensive, and ITO is on a flexible substrate. It is unstable and not resistant to bending, so it is hoped to develop alternative materials. The transmittance of carbon nanotubes is superior to ITO only in the infrared region. Under current process conditions, graphene is not as conductive as Ag, Ni, etc., but graphene has good flexibility. The metal film is excellent in conductivity and light transmittance, but is unstable on a flexible substrate. Summary of the invention
本发明的目的是为了克服现有透明电极材料透过率低， 电阻率较高， 缺乏柔性而 不耐挠曲的缺点， 提供一种透过率高、 导电性能好， 柔韧性优异的金属膜与石墨烯复合 的透明电极材料及其制备方法。  The object of the present invention is to overcome the shortcomings of the prior transparent electrode materials such as low transmittance, high resistivity, lack of flexibility and resistance to flexing, and a metal film having high transmittance, good electrical conductivity and excellent flexibility. Transparent electrode material composited with graphene and preparation method thereof.
本发明提供一种透明电极材料， 所述透明电极材料包括基片和附着在该基片上的 导电层， 该导电层含有石墨烯与金属， 所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述 导电层的在可见光区域的透光率为 70-98%， 在红外光区域的透光率为 70-98%。  The present invention provides a transparent electrode material, the transparent electrode material comprising a substrate and a conductive layer attached to the substrate, the conductive layer containing graphene and a metal, and the sheet resistance of the conductive layer is ΙΟΟΟΩ/sq or less. 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%.
本发明还提供上述透明电极材料的制备方法， 该方法包括， 在基片上形成导电层， 该导电层含有石墨烯与金属， 所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述导电层在 可见光区域的透光率为 70-98%， 在红外光区域的透光率为 70-98%。  The present invention also provides a method for preparing the above transparent electrode material, the method comprising: forming a conductive layer on a substrate, the conductive layer containing graphene and a metal, the conductive layer having a sheet resistance of ΙΟΟΟΩ/sq or less, the conductive layer being The light transmittance in the visible light region is 70-98%, and the light transmittance in the infrared light region is 70-98%.
本发明的透明电极因为含有金属和石墨烯的复合结构， 使得其不仅具有高透光性、 低电阻的优异性能， 并且因为石墨烯的加入加强了透明电极的结构稳定性和耐弯曲性， 从而进一步增加了电子传输通道， 最终改善了透明电极的导电性（推测这是因为石墨烯 薄膜的柔性， 可以改善金属膜在基片上的性能； 石墨烯的导电性， 在与金属膜复合后可 以起到电子桥梁的作用， 进一步增加金属膜的导电性； 而石墨烯在紫外、 可见光、 红外 光区透过率都很高， 不会影响金属膜的透光性）。 Since 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 electrical resistance, but also because the addition of graphene enhances structural stability and bending resistance of the transparent electrode, Further increasing the electron transport channel, ultimately improving the conductivity of the transparent electrode (presumably because of graphene The flexibility of the film can improve the performance of the metal film on the substrate; the conductivity of the graphene can act as an electron bridge after compounding with the metal film to further increase the conductivity of the metal film; and the graphene is in the ultraviolet, visible, The transmittance of the infrared light region is high, and does not affect the light transmittance of the metal film).
本发明的透明电极材料在光电器件、 光电探测器以及半导体发光， 尤其在柔性太 阳能电池、 柔性显示器等柔性器件方面用途广泛。 本发明的制备方法工艺简单， 易于实 现工业化生产。 附图说明  The transparent electrode material of the present invention is widely used in photovoltaic devices, photodetectors, and semiconductor light-emitting devices, particularly flexible devices such as flexible solar cells and flexible displays. The preparation method of the invention is simple in process and easy to realize industrial production. DRAWINGS
图 1是 a型透明电极材料的示意图。  Figure 1 is a schematic illustration of a type a transparent electrode material.
图 2是 b型透明电极材料的示意图。  Figure 2 is a schematic illustration of a b-type transparent electrode material.
图 3是另一种 b型透明电极材料的示意图。  Figure 3 is a schematic illustration of another b-type transparent electrode material.
图 4-7是本发明的 a型或 b型透明电极材料的主视图和左 （右） 视图。 附图标记说明  4-7 are a front view and a left (right) view of a type a or b type transparent electrode material of the present invention. Description of the reference numerals
1为基片； 2为金属层； 3为石墨烯层； 4为由石墨烯和金属的混合物形成的导电 层。 具体实施方式  1 is a substrate; 2 is a metal layer; 3 is a graphene layer; and 4 is a conductive layer formed of a mixture of graphene and a metal. detailed description
本发明提供一种透明电极材料， 该材料包括基片和附着在该基片上的导电层， 该 导电层含有石墨烯与金属， 所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述导电层的在 可见光区域的透光率为 70-98%， 在红外光区域的透光率为 70-98%; 优选情况下， 所述 导电层的方块电阻为 ΙΟΟΩ/sq 以下， 所述导电层的在可见光区域的透光率为 80-98%， 在红外光区域的透光率为 80-98%。  The present invention provides a transparent electrode material comprising a substrate and a conductive layer attached to the substrate, the conductive layer containing graphene and a metal, the conductive layer having a sheet resistance of ΙΟΟΟΩ/sq or less, 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%; preferably, the conductive layer has a sheet resistance of ΙΟΟΩ/sq or less, the conductive layer The light transmittance in the visible light region is 80-98%, and the light transmittance in the infrared light region is 80-98%.
在本发明的透明电极材料中， 所述含有石墨烯与金属的导电层的实现方式可以有 多种， 例如可以是由石墨烯与金属的混合物层形成， 也可以是由石墨烯层和金属层交替 性形成， 还可以是由石墨烯与金属的混合物层与石墨烯层或金属层交替形成， 其中优选 为由石墨烯与金属的混合物层形成或由石墨烯层和金属层交替性形成。  In the transparent electrode material of the present invention, the conductive layer containing graphene and metal may be implemented in various forms, for example, may be formed of a mixture layer of graphene and metal, or may be composed of a graphene layer and a metal layer. Alternatively, it may be formed by alternately forming a mixture layer of graphene and metal with a graphene layer or a metal layer, preferably formed of a mixture layer of graphene and metal or alternately formed of a graphene layer and a metal layer.
优选情况下， 本发明的透明电极材料中的所述导电层由石墨烯与金属的混合物层 形成时， 所述石墨烯和金属的重量比可以为 1 :0.01-10000， 所述石墨烯与金属的混合物 层的层数可以为 1-20层，每一层所述石墨烯与金属的混合物层的厚度可以为 0.2-300nm; 为了获得更好的透光性和挠性， 优选情况下， 所述石墨烯和金属的重量比优选为 1 :0.1-1000, 每一层所述石墨烯与金属的混合物层的厚度优选为 0.2-100nm。 本发明中， 所述石墨烯与金属的混合物层指的是由石墨烯与金属的混合物形成的层。 Preferably, when the conductive layer in the transparent electrode material of the present invention is formed of a mixture layer of graphene and metal, the weight ratio of the graphene to the metal may be 1:0.01-10000, the graphene and the metal The layer of the mixture layer may be 1-20 layers, each layer of the mixture of graphene and metal may have a thickness of 0.2-300 nm; In order to obtain better light transmittance and flexibility, preferably, the weight ratio of the graphene to the metal is preferably 1:0.1 to 1000, and the thickness of the layer of the mixture of the graphene and the metal in each layer is preferably 0.2. -100nm. In the present invention, the layer of the mixture of graphene and metal refers to a layer formed of a mixture of graphene and metal.
同样优选情况下， 本发明的透明电极材料中的所述导电层由石墨烯层和金属层交 替性形成时， 所述石墨烯层的厚度可以为 0.2-10nm， 所述石墨烯层的层数可以为 1-10 层， 所述金属层的厚度可以为 0.2-300nm， 所述金属层的层数可以为 1-10层。 为了获得 更好的透光率和挠性， 优选情况下， 所述石墨烯层的厚度为 0.2-3nm， 所述石墨烯层的 层数可以为 1-2层； 所述金属层的厚度为 0.5-100nm， 所述金属层的层数可以为 1-2层。 需要明确的是， 上述厚度分别指石墨烯层和金属层的平均厚度。  Also preferably, when the conductive layer in the transparent electrode material of the present invention is formed by alternating graphene layers and metal layers, the thickness of the graphene layer may be 0.2-10 nm, and the number of layers of the graphene layer It may be 1-10 layers, the metal layer may have a thickness of 0.2-300 nm, and the metal layer may have a layer number of 1-10 layers. In order to obtain better light transmittance and flexibility, the thickness of the graphene layer is preferably 0.2-3 nm, and the number of layers of the graphene layer may be 1-2 layers; the thickness of the metal layer is The number of layers of the metal layer may be 1-2 layers from 0.5 to 100 nm. It is to be understood that the above thicknesses refer to the average thickness of the graphene layer and the metal layer, respectively.
本发明的透明电极材料中的导电层的每一层均可以是图案化的也可以是非图案化 的。  Each of the conductive layers in the transparent electrode material of the present invention may be patterned or unpatterned.
优选情况下， 本发明中的所述金属层为图案化的金属膜， 所述金属膜优选为选自 由微纳金属环组成的连续金属膜、 由微纳金属环组成的不连续金属膜、 由规则孔排列形 成的二维金属微网格、 由不规则孔排列形成的二维金属微网格、 由连续金属岛组成的金 属膜、 由不连续金属岛组成的金属膜和由一维金属纳米线组成的金属膜中的一种。 为了 得到更好的导电性，透光性和挠性，进一步优选为由规则孔排列形成的二维金属微网格。  Preferably, the metal layer in the present invention is a patterned metal film, and the metal film is preferably a continuous metal film selected from a micro-nano metal ring, a discontinuous metal film composed of a micro-nano metal ring, a two-dimensional metal microgrid formed by regular pore arrangement, a two-dimensional metal microgrid formed by irregular pore arrangements, a metal film composed of continuous metal islands, a metal film composed of discontinuous metal islands, and a one-dimensional metal nanometer One of the metal films composed of wires. In order to obtain better conductivity, light transmittance and flexibility, a two-dimensional metal microgrid formed by regular pore arrangement is further preferable.
在本发明的透明电极材料中， 所述金属可以为选自银、 铜、 金、 铝、 镍、 铂、 锌、 锡、 铁、 钴、 锰、 钼和钛中的一种或多种， 优选为金或银。  In the transparent electrode material of the present invention, the metal may be one or more selected from the group consisting of silver, copper, gold, aluminum, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, preferably It is gold or silver.
本发明中所涉及的石墨烯可以为本领域常规使用的各种石墨烯， 本发明对所述石 墨烯的层数无特殊要求， 可以为单层石墨烯和多层石墨烯的混合物， 所述多层的石墨烯 一般为 2-10层的多层石墨烯， 另外， 所述石墨烯为全部由碳原子组成的石墨烯或掺杂 有杂原子的石墨烯。其中， 所述掺杂有杂原子的石墨烯中的杂原子可以选自氮、氧、硫、 硼和磷中的一种或多种。  The graphene involved in the present invention may be various graphenes conventionally used in the art, and the present invention has no particular requirement on the number of layers of the graphene, and may be a mixture of a single layer of graphene and a plurality of graphenes. The multilayer graphene is generally 2-10 layers of multilayer graphene, and the graphene is graphene composed entirely of carbon atoms or graphene doped with hetero atoms. The hetero atom in the graphene doped with a hetero atom may be selected from one or more of nitrogen, oxygen, sulfur, boron, and phosphorus.
在本发明中， 可以根据不同的需求选择不同的基片， 可以为柔性基片也可以为非 柔性基片， 优选情况下， 在本发明的透明电极材料中， 所述基片可以为在可见光区域的 透光率为 90-100%，优选为 92-98%、在红外光区域的透光率为 90-100%，优选为 92-98% 的透明高分子膜、 玻璃和石英中的一种或多种， 所述透明高分子膜可以为聚乙烯醇膜、 聚酰亚胺膜、 聚对苯二甲酸乙二酯膜、 聚氯乙烯膜、 聚碳酸酯膜、 聚氨酯膜和聚丙烯酸 酯膜中的一种或多种。  In the present invention, different substrates may be selected according to different needs, and may be a flexible substrate or a non-flexible substrate. Preferably, in the transparent electrode material of the present invention, the substrate may be in visible light. The light transmittance of the region is 90-100%, preferably 92-98%, and the light transmittance in the infrared light region is 90-100%, preferably 92-98%, one of transparent polymer film, glass and quartz. The transparent polymer film may be a polyvinyl alcohol film, a polyimide film, a polyethylene terephthalate film, a polyvinyl chloride film, a polycarbonate film, a polyurethane film, and a polyacrylate. One or more of the membranes.
优选情况下， 本发明提供的透明电极材料上的导电层有三种类型， 一种为石墨烯 和金属形成的混合物层， 另一种为交替的先形成石墨烯层， 再形成金属层， 还有一种为 交替的先形成金属层， 再形成石墨烯层， 根据制备方法可以将后两者划分为一类。 Preferably, the conductive layer provided on the transparent electrode material of the present invention has three types, one is graphene. a mixture layer formed of a metal, the other is an alternating first graphene layer, and then a metal layer, and an alternate first metal layer is formed, and then a graphene layer is formed, and the latter two can be divided according to a preparation method. For a class.
因此， 本发明针对不同类型的导电层， 提供了两种相应的制备方法。  Thus, the present invention provides two corresponding methods of preparation for different types of conductive layers.
本发明提供了上述导电层由金属和石墨烯的混合物层形成的透明电极材料的制备 方法， 该方法包括， 在基片形成导电层， 所述导电层由石墨烯和金属的混合物层形成， 形成的所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述导电层在可见光区域的透光率为 70-98%, 在红外光区域的透光率为 70-98%。  The present invention provides a method for preparing a transparent electrode material in which the above conductive layer is formed of a mixture layer of metal and graphene, the method comprising: forming a conductive layer on a substrate, the conductive layer being formed of a mixture layer of graphene and a metal, forming The sheet resistance of the conductive layer is ΙΟΟΟΩ/sq or less, and 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%.
本发明对所述在基片上形成导电层的方法无特殊要求， 例如可以按如下步骤进行: 将含有石墨烯和金属的分散液附着在基片表面， 在 60-200°C下放置 l-120min后， 冷却 至室温（10-40°C )， 然后重复进行 0-19次以下步骤： 将含有石墨烯和金属的分散液附着 在所得到的石墨烯和金属的混合物层的表面， 在 60-200°C下放置 l-120min后， 冷却至 室温 （10-40°C ): 得到带有导电层的透明电极材料。 其中， 重复进行步骤可以根据需要 来确定是否进行， 以及进行的次数， 通过上述步骤， 可以在透明基底上形成 1-20层的 导电层。  The present invention has no special requirement for the method of forming a conductive layer on a substrate, for example, the following steps can be performed: attaching a dispersion containing graphene and a metal to the surface of the substrate, and placing it at 60-200 ° C for l-120 min. Thereafter, cooling to room temperature (10-40 ° C), and then repeating the steps of 0-19 times: attaching a dispersion containing graphene and a metal to the surface of the obtained layer of the mixture of graphene and metal, at 60- After standing at 200 ° C for l-120 min, it was cooled to room temperature (10-40 ° C): A transparent electrode material with a conductive layer was obtained. Wherein, the steps may be repeated to determine whether or not to proceed, and the number of times of the process. Through the above steps, a conductive layer of 1-20 layers may be formed on the transparent substrate.
在上述制备方法中， 所述含有石墨烯与金属的分散液中的石墨烯的浓度可以为 0.001-lOmg/mL, 金属的浓度可以为 0.01-lOOmg/mL; 为了方便操作， 所述含有石墨烯 与金属的分散液中石墨烯的浓度优选为 0.01-lmg/mL，金属的浓度优选为 0.1-10mg/mL。  In the above preparation method, the concentration of graphene in the dispersion containing graphene and metal may be 0.001 to 10 mg/mL, and the concentration of metal may be 0.01 to 100 mg/mL; for convenience of operation, the graphene is contained. The concentration of graphene in the dispersion with the metal is preferably 0.01-1 mg/mL, and the concentration of the metal is preferably 0.1-10 mg/mL.
本发明对所述分散液中的分散介质无特殊要求， 可以参照现有技术进行， 例如可 以为水和常用的用于制备含有石墨烯的分散液使用的有机溶剂， 在此不再赘述。 本发明 中的分散液可以为各种形式， 只要所述金属和石墨烯在分散液中均匀分布即可， 例如可 以为溶胶形式、 溶液形式等。  The present invention has no particular requirement for the dispersion medium in the dispersion, and can be carried out by referring to the prior art. For example, it can be water and a common organic solvent used for preparing a dispersion containing graphene, and will not be described herein. The dispersion liquid in the present invention may be in various forms as long as the metal and graphene are uniformly distributed in the dispersion, and may be, for example, a sol form, a solution form or the like.
本发明中， 分散液中的金属颗粒的大小的可选范围较宽， 本领域技术人员根据本 发明记载的技术方案可以很容易进行选择，优选为微米级和 /或纳米级，更优选为纳米级。  In the present invention, the range of the size of the metal particles in the dispersion is wide, and those skilled in the art can easily select according to the technical solution described in the present invention, preferably on the order of micrometers and/or nanometers, more preferably nanometers. level.
优选情况下， 每一次含有石墨烯与金属的分散液的用量为使获得的透明电极材料 中每一层所述含有石墨烯与金属的混合物层的厚度为 0.2-300nm。  Preferably, the dispersion containing graphene and metal is used in an amount such that the layer containing the mixture of graphene and metal in each of the obtained transparent electrode materials has a thickness of 0.2 to 300 nm.
在本发明中， 将通过该方法制备的透明电极材料称为 a型透明电极材料。 如图 1 所示， 其中， 1为基片； 4为由石墨烯和金属的混合物形成的导电层， 图 1只图示了本 发明一种实施方式中的两层的透明电极材料， 本领域技术人员可以确定， 更多的由石墨 烯和金属的混合物形成的导电层可以在由石墨烯和金属的混合物形成的导电层之上依 次形成。 在上述制备方法中， 将含有石墨烯和金属的分散液附着在透明基底表面或者附着 在所得到的石墨烯和金属的混合物层的表面的方法没有特别的限定，例如可以为选自旋 涂法、 喷涂法、 刮涂法和浸渍法中的一种或多种， 优选为旋涂法。 In the present invention, the transparent electrode material prepared by this method is referred to as an a-type transparent electrode material. As shown in FIG. 1, wherein 1 is a substrate; 4 is a conductive layer formed of a mixture of graphene and metal, and FIG. 1 only illustrates a two-layer transparent electrode material in an embodiment of the present invention, The skilled person can determine that more conductive layers formed from a mixture of graphene and metal can be formed sequentially over the conductive layer formed from a mixture of graphene and metal. In the above preparation method, a method of attaching a dispersion containing graphene and a metal to the surface of a transparent substrate or adhering to the surface of the obtained mixture layer of graphene and metal is not particularly limited, and for example, may be selected from a spin coating method. One or more of a spray coating method, a knife coating method, and a dipping method, preferably a spin coating method.
根据本发明的方法， 所述石墨烯和金属的分散液可以以各种形式提供， 例如溶胶 形式，所述含有石墨烯和金属的分散液可以参照现有技术进行制备，本发明无特殊要求， 在此不再赘述。  According to the method of the present invention, the dispersion of graphene and metal may be provided in various forms, such as a sol form, and the dispersion containing graphene and metal may be prepared according to the prior art, and the present invention has no special requirements. I will not repeat them here.
本发明还提供上述导电层由石墨烯层和金属层交替形成的透明电极材料的制备方 法， 该方法包括， 在基片上交替形成金属层和石墨烯层， 以在基片上形成导电层， 所述 导电层的方块电阻为 ΙΟΟΟΩ/sq以下， 所述导电层在可见光区域的透光率为 70-98%， 在 红外光区域的透光率为 70-98%。  The present invention also provides a method for preparing a transparent electrode material in which the conductive layer is alternately formed of a graphene layer and a metal layer, the method comprising: alternately forming a metal layer and a graphene layer on the substrate to form a conductive layer on the substrate, The sheet resistance of the conductive layer is ΙΟΟΟΩ/sq or less, 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%.
在本发明中， 将导电层由石墨烯层和金属层交替形成的透明电极材料称为 b型透 明电极材料， 其中包括在基片上先形成石墨烯层后形成金属层的透明电极材料， 如图 2 所示， 其中， 1为基片； 2为金属层； 3为石墨烯层； 和在基片上先形成金属层后形成石 墨烯层的透明电极材料， 如图 3所示， 其中， 1为基片； 2为金属层; 3为石墨烯层。 图 2和图 3只是分别图示了本发明两种实施方式中的两层的透明电极材料， 本领域技术人 员可以确定， 更多的石墨烯层或金属层可以在金属层和石墨烯层之上依次形成。  In the present invention, the transparent electrode material in which the conductive layer is alternately formed of the graphene layer and the metal layer is referred to as a b-type transparent electrode material, and includes a transparent electrode material which forms a metal layer after forming a graphene layer on the substrate, as shown in the figure. 2, wherein 1 is a substrate; 2 is a metal layer; 3 is a graphene layer; and a transparent electrode material forming a graphene layer after forming a metal layer on the substrate, as shown in FIG. 3, wherein 1 is The substrate; 2 is a metal layer; 3 is a graphene layer. 2 and 3 are only two layers of transparent electrode materials in two embodiments of the present invention, respectively, and those skilled in the art can determine that more graphene layers or metal layers can be in the metal layer and the graphene layer. It is formed in order.
根据本发明的方法， 优选情况下， 所述金属层的厚度可以为 0.2-300nm， 优选为 0.5-100nm, 所述金属层的层数可以为 1-10层， 优选为 1-2层； 所述石墨烯层的厚度可 以为 0.2-10nm， 优选为 0.2-3nm; 所述石墨烯层的层数可以为 1-10层， 优选为 1-2层。  According to the method of the present invention, preferably, the metal layer may have a thickness of 0.2-300 nm, preferably 0.5-100 nm, and the metal layer may have a layer number of 1-10 layers, preferably 1-2 layers; The thickness of the graphene layer may be from 0.2 to 10 nm, preferably from 0.2 to 3 nm; the number of layers of the graphene layer may be from 1 to 10 layers, preferably from 1 to 2 layers.
在上述制备方法中， 对所述形成石墨烯层的方法没有特别的限定， 可以参照现有 技术进行， 例如可以为选自旋涂法、喷涂法、刮涂法、浸渍法或提拉法， 优选为旋涂法； 对所述形成金属层的方法也没有特别的限定， 例如可以为选自模板法、 电纺织法、 压印 法、 自组装法、 刻蚀法、 沉积法、 电磁场引导法、 溅射法、 溶胶凝胶法、 旋涂法、 喷涂 法、 静电纺丝或刮涂法， 优选为模板法。  In the above preparation method, the method for forming the graphene layer is not particularly limited and may be carried out by referring to the prior art, and may be, for example, selected from a spin coating method, a spray coating method, a knife coating method, a dipping method or a pulling method. Preferably, the method of forming the metal layer is not particularly limited, and may be, for example, selected from the group consisting of a stencil method, an electrospinning method, an imprint method, a self-assembly method, an etching method, a deposition method, and an electromagnetic field guiding method. The sputtering method, the sol-gel method, the spin coating method, the spray coating method, the electrospinning or the doctor blade method are preferably a template method.
由于在本发明的制备方法中所使用的金属、 基片、 以及构成导电层的所述石墨烯 与金属的混合物层、石墨烯层的厚度和种类等均与产品中所涉及的相同，在此不再赘述。  Since the metal, the substrate, and the mixture of the graphene and the metal constituting the conductive layer, the thickness and the kind of the graphene layer, etc., which are used in the production method of the present invention are the same as those involved in the product, No longer.
下面结合实施例对本发明进行进一步说明。  The invention is further illustrated by the following examples.
在以下实施例中， 用紫外 /可见 /近红外分光光度计（PerkinElmer Lambda 950)测定 可见光透过率和红外光透过率； 用双电测四探针测试仪（广州四探针科技 RTS-9)测定 方块电阻； 薄膜厚度用扫描探针显微镜测试 （Digital Instruments Dimension 3100)； 用 SEM扫描电镜 （日本日立公司， Hitachi S-4800) 测试材料的表面形貌， 尺寸 （如平均 粒径等）。 制备例 1 In the following examples, the visible light transmittance and the infrared light transmittance were measured by an ultraviolet/visible/near infrared spectrophotometer (PerkinElmer Lambda 950); the four-probe tester with a double electric test (Guangzhou four-probe technology RTS- 9) Determine the sheet resistance; the film thickness is tested with a scanning probe microscope (Digital Instruments Dimension 3100); SEM scanning electron microscopy (Hitachi, Hitachi S-4800, Japan) was used to test the surface morphology and size (such as average particle size) of the material. Preparation Example 1
氧化石墨烯溶胶的制备  Preparation of graphene oxide sol
向 1500g 的浓度为 98 重量％的浓硫酸中加入 5.0g 的天然鳞片状石墨 （粒径为 200μηι)、 5.0g的硝酸钠和 25.0g的高锰酸钾， 将所得混合物在 0°C的冰浴条件下 （即通 过冰浴使混合物的温度为 0°C )搅拌 5h后， 接着再在 30°C下搅拌 10h; 然后向所得混合 物中加入 500mL水进行稀释， 接着升温至 70°C并搅拌 2h后， 加入 6mL的浓度为 30重 量％的双氧水， 搅拌 lh后过滤， 然后将得到的滤饼用浓度为 10重量％的盐酸离心洗涤， 接着再用去离子水离心洗涤，将洗涤后的胶状产物加入到 40mL的去离子水中，在 200W 的功率下超声分散得到氧化石墨烯溶胶 （氧化石墨烯的含量为 20 重量％， 水的含量为 80重量％)。 实施例 1  To 1500 g of concentrated sulfuric acid having a concentration of 98% by weight, 5.0 g of natural flaky graphite (having a particle size of 200 μm), 5.0 g of sodium nitrate and 25.0 g of potassium permanganate were added, and the resulting mixture was iced at 0 ° C. The mixture was stirred under a bath condition (i.e., the temperature of the mixture was 0 ° C by an ice bath) for 5 hours, and then further stirred at 30 ° C for 10 hours; then 500 mL of water was added to the resulting mixture for dilution, followed by raising the temperature to 70 ° C and stirring. After 2 h, 6 mL of hydrogen peroxide at a concentration of 30% by weight was added, stirred for 1 h, and then filtered, and then the obtained filter cake was washed with a concentration of 10% by weight of hydrochloric acid, followed by centrifugation with deionized water, and the washed gel was washed. The product was added to 40 mL of deionized water and 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
本实施例是为说明本发明的 b型透明电极材料的制备方法。  This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
( 1 )制备多孔阳极氧化铝模板:采用两步阳极氧化法 (根据 Hideki Masuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb structures of Anodic Alumina, SCIENCE, 268( 9) 1995 )中提供的方法）制备多孔阳极氧化 铝片， 通过扫描电镜测出该多孔阳极氧化铝片的孔径为 50nm， 孔间距为 150nm;  (1) Preparation of a porous anodized aluminum oxide template: using a two-step anodizing method (according to Hideki Masuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb structures of Anodic Alumina, SCIENCE, 268(9) 1995) The method provided in the method) preparing a porous anodized aluminum sheet, the porous anodized aluminum oxide sheet having a pore diameter of 50 nm and a pore spacing of 150 nm as determined by scanning electron microscopy;
(2) 电子束蒸镀金属层： 用电子束蒸发仪 （Edwars, AUTO 500) 向步骤 （1 ) 得 到的阳极氧化铝片上蒸镀一层金属银， 厚度 3nm;  (2) Electron beam evaporation metal layer: an electron beam evaporator (Edwars, AUTO 500) is used to vaporize a layer of metallic silver on the anodized aluminum sheet obtained in step (1) to a thickness of 3 nm;
( 3 ) 去除氧化铝模板： 在步骤 （2) 蒸镀有金属银的阳极氧化铝片下方放置石英 片 （锦州华美石英电器厂， 大小为 2Cmx2cm， 厚度为 lmm)， 在浓度为 1%的磷酸溶液 中溶解掉阳极氧化铝， 带孔金属银网格自然沉降到石英片上； 用去离子水洗涤石英片上 多余的磷酸和金属离子， 100°C下干燥 4h; (3) Removal of the alumina template: Place the quartz plate under the anodized aluminum sheet with metal silver vapor deposited in step (2) (Jinzhou Huamei Quartz Electric Factory, size 2 C mx2cm, thickness lmm) at a concentration of 1% The anodized aluminum is dissolved in the phosphoric acid solution, and the porous metal silver mesh is naturally deposited on the quartz plate; the excess phosphoric acid and metal ions on the quartz plate are washed with deionized water, and dried at 100 ° C for 4 h;
(4 ) 制备氧化石墨烯薄膜： 在步骤 （3 ) 得到的有金属网格的石英片上用旋涂仪 以 4000rpm的转速旋涂一层 6nm厚的制备例 1中得到的氧化石墨烯溶胶， 100°C下干燥 lOmin;  (4) Preparation of a graphene oxide film: a 6 nm thick graphene oxide sol obtained in Preparation Example 1 was spin-coated on a quartz plate having a metal mesh obtained in the step (3) by a spin coater at 4000 rpm. Drying at ° C for 10 min;
( 5 ) 热还原氧化石墨烯： 在 Ar气保护下， 将步骤 （4) 得到的含有厚度为 0.8nm 的氧化石墨烯薄膜的石英片放入石英管， 然后将石英管放入管式炉中， 以升温速率每小 时 200°C缓慢升温到 800°C加热 10min， 然后在 Ar气保护下在炉中缓慢冷却至室温， 还 原得到含有石墨烯与金属银的透明电极材料。 透明电极材料的主视图和左 （右）视图如 图 4中的 A和 B所示。 (5) Thermal reduction of graphene oxide: under Ar gas protection, the thickness of step (4) is 0.8 nm The quartz sheet of the graphene oxide film is placed in a quartz tube, and then the quartz tube is placed in a tube furnace, and the temperature is slowly raised to 800 ° C per hour at a heating rate of 10 ° C for 10 min, and then in the furnace under the protection of Ar gas. The mixture was slowly cooled to room temperature, 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 as A and B in FIG.
透明电极材料的金属层厚度为 3nm， 金属层层数为 1层； 石墨烯层厚度为 0.8nm， 石墨烯层层数为 1层。  The thickness of the metal layer of the transparent electrode material is 3 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene layer is 0.8 nm, and the number of layers of the graphene layer is 1 layer.
透明电极材料在可见光区透光率为 92%、红外光区透光率为 92%、方块电阻 5Q/sq。 实施例 2  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 5 Q/sq. Example 2
本实施例是为说明本发明的 b型透明电极材料的制备方法。  This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
( 1 )化学气相沉积的方法制备氮掺杂石墨烯： 用镀膜机（KYUY中科科仪技术发 展有限责任公司， 型号 SBC-2) , 以 M为靶材料， 沉积时间 20s， 在石英片 （锦州华美 石英电器厂， 大小为 2cmx2cm， 厚度为 lmm) 上热蒸镀 50nm厚的 Ni。 将石英片放入 石英管中， 通氢气 （20sccm) 和氩气 （lOOsccm), 当炉体中心温度升高到 800 °C时， 通 入 60sccm的 CH4和 60sccm的 NH3， 将石英管放入炉体中心， lOmin后， 将样品在氢气 流下冷却到室温，得到氮掺杂的石墨烯薄膜，用浓度为 1%的磷酸溶液溶解薄膜上的 Ni， 用去离子水洗涤石墨烯表面三次。 (1) Preparation of nitrogen-doped graphene by chemical vapor deposition: using a coating machine (KYUY Science and Technology Development Co., Ltd., model SBC-2), with M as the target material, deposition time 20s, in quartz plate ( Jinzhou Huamei Quartz Electric Appliance Factory, size 2cmx2cm, thickness lmm) is hot-deposited with 50nm thick Ni. Put the quartz plate into the quartz tube, pass hydrogen gas (20sccm) and argon gas (100cmcm). When the center temperature of the furnace body rises to 800 °C, pass 60sccm of CH 4 and 60sccm of NH 3 and place the quartz tube. After entering the center of the furnace, after lOmin, the sample was cooled to room temperature under a hydrogen stream to obtain a nitrogen-doped graphene film, and the Ni on the film was dissolved in a phosphoric acid solution having a concentration of 1%, and the surface of the graphene was washed three times with deionized water.
(2) 制备聚苯乙烯微球： 在 500mL三口烧瓶中加入 10mL苯乙烯和 150mL水， 通氮气排空气 15min， 恒温水浴 70°C下搅拌 20min， 加入 0.2g过硫酸钾， 70°C下反应 24ho 离心分离得到聚苯乙烯微球单分散水溶液 （苯乙烯微球浓度为 10重量％， 苯乙烯 微球的平均粒径为 1.3μηι)。  (2) Preparation of polystyrene microspheres: Add 10 mL of styrene and 150 mL of water to a 500 mL three-necked 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. A monodisperse aqueous solution of polystyrene microspheres (concentration of styrene microspheres of 10% by weight and average particle diameter of styrene microspheres of 1.3 μm) was obtained by centrifugation at 24 ho.
( 3 ) 以聚苯乙烯微球单层膜为模板制备图案化金属薄膜： 向 4.95mL聚苯乙烯微 球单分散水溶液 （苯乙烯微球浓度为 10重量％) 中加入 0.05mL苯乙烯和 5mL无水乙 醇， 再向该溶液中加入 0.15 L的硫酸（浓度是 98重量％)， 超声 15min， 在容器底部放 入上述步骤 （1 ) 处理的表面有石墨烯薄膜的石英片， 放走容器中的液体， 用去离子水 洗涤三次。用等离子刻蚀（RIE)***（SENTECH, ETCHCAB200), 用氧离子刻蚀 10s， 聚苯乙烯微球粒径减小到 1μηι。 用磁控溅射仪 （ULVAC Inc, ACS-400-C4), 在工作压 强 0.5Pa， 功率 40W条件下， 与石英片垂直溅射 10s， 在聚苯乙烯微球空隙中沉积金属 Al， 得到 3nm厚的 Al， 孔间距 600nm， 孔径 1μηι。 将前述沉积有金属的石英片浸入甲 苯溶液中溶解模板聚苯乙烯微球后， 并用去离子水洗涤，得到含有金属铝和 Ν掺杂的石 墨烯的透明电极材料。 透明电极材料的主视图和左 （右） 视图如图 5中的 A和 B所示。 透明电极材料的金属层厚度为 3nm， 金属层层数为 1层； 石墨烯厚度为 1.2nm， 石 墨烯层层数为 1层。 (3) Preparing a patterned metal film using a polystyrene microsphere monolayer as a template: To a 4.95 mL polystyrene microsphere monodisperse aqueous solution (styrene microsphere concentration of 10% by weight), 0.05 mL of styrene and 5 mL were added. Anhydrous ethanol was added to the solution, and 0.15 L of sulfuric acid (concentration: 98% by weight) was added to the solution, and ultrasonication was carried out for 15 minutes. At the bottom of the container, a quartz sheet having a graphene film treated on the surface of the above step (1) was placed, and the container was discharged. The liquid was 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 the polystyrene microspheres was reduced to 1 μm. Using a magnetron sputtering device (ULVAC Inc, ACS-400-C4), under the condition of working pressure 0.5Pa, power 40W, it was sputtered perpendicularly with the quartz plate for 10 s, and metal Al was deposited in the gap of the polystyrene microsphere to obtain 3 nm. Thick Al, with a hole pitch of 600 nm and a pore size of 1 μm. The metal plated quartz plate is immersed in a toluene solution to dissolve the template polystyrene microspheres, and washed with deionized water to obtain a metal containing aluminum and lanthanum doped stone. A transparent electrode material of ocene. The front view and left (right) view of the transparent electrode material are shown as A and B in FIG. The thickness of the metal layer of the transparent electrode material is 3 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene is 1.2 nm, and the number of layers of the graphene layer is 1 layer.
透明电极材料的可见光透过率为 98%、 红外光透过率 98%、 方块电阻 3Q/sq。 实施例 3  The transparent electrode material has a visible light transmittance of 98%, an infrared light transmittance of 98%, and a sheet resistance of 3Q/sq. Example 3
本实施例是为说明本发明的 b型透明电极材料的制备方法。  This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
( 1 )石墨烯溶胶的制备： 15g水中溶解 600mg硼氢化钠， 将得到的硼氢化钠溶液 加入 50mL制备例 1中得到的氧化石墨烯溶胶中，用 5重量％的碳酸钠溶液调节溶液 pH 值至 9， 将这些混合物在 80°C下搅拌 lh， 然后用去离子水在 5000rpm的转速下离心洗 涤 5次， 将洗涤后的石墨烯溶解在 1 :1 的水和乙醇混合溶液中， 得到浓度为 10mg/mL 的石墨烯溶胶。  (1) Preparation of graphene sol: 600 mg of sodium borohydride was dissolved in 15 g of water, and the obtained sodium borohydride solution was added to 50 mL of the graphene oxide sol obtained in Preparation Example 1, and the pH value of the solution was adjusted with a 5% by weight sodium carbonate solution. To 9, the mixture was stirred at 80 ° C for 1 h, then centrifuged 5 times with deionized water at 5000 rpm, and the washed graphene was dissolved in a 1:1 mixture of water and ethanol to obtain a concentration. It is a 10 mg/mL graphene sol.
(2)石墨烯薄膜的制备：采用浸渍提拉法，将聚对苯二甲酸乙二醇酯薄膜 PET (日 本艾克 AICA, 型号 HC2106, 大小为 2cmx2cm， 厚度 0.188mm)浸入步骤（1 )得到的 石墨烯溶胶中， 然后以与水平面垂直的方向将 PET 匀速提拉出液面， 用去离子水洗涤 PET背面多余的石墨烯溶胶， 室温下晾干， 得到石墨烯层， 厚度为 7nm。  (2) Preparation of graphene film: The polyethylene terephthalate film PET (Japan Aike, model HC2106, size 2cmx2cm, thickness 0.188mm) was immersed in step (1) by immersion pulling method. In the graphene sol, the PET is uniformly pulled out of the liquid surface in a direction perpendicular to the horizontal plane, and the excess graphene sol on the back side of the PET is washed with deionized water, and dried at room temperature to obtain a graphene layer having a thickness of 7 nm.
(3 ) 紫外光刻的方法制备光刻胶模板： 采用紫外光刻的方法， 先在步骤 （2) 得 到的石墨烯层上用旋涂仪旋涂 5mL光刻胶（公司 ALLRESIST, 型号 AR-N4340), 然后 在暗室中在光刻胶上放置带垂直纳米线网格图案的模板 （购买于中科院半导体研究所） 紫外曝光， 在显影液 （ALLRESIST厂家， 型号 AR300-26)作用下光刻胶图案化刻蚀得 到模板纳米线网格图案。在扫描电镜下检测，光刻胶纳米线的宽度为 2μηι，线间距 20μηι。  (3) Preparation of photoresist template by ultraviolet lithography method: Using ultraviolet lithography method, spin-coating 5 mL of photoresist on the graphene layer obtained in step (2) (company ALLRESIST, model AR-N4340) Then, a template with a vertical nanowire grid pattern (purchased at the Institute of Semiconductors, Chinese Academy of Sciences) is placed on the photoresist in a dark room. UV exposure, photoresist patterning under the action of developer (ALLRESIST manufacturer, model AR300-26) Etching results in a template nanowire grid pattern. Under the scanning electron microscope, the width of the photoresist nanowires was 2 μm, and the line pitch was 20 μm.
(4) 在光刻胶空隙中蒸镀 Cu: 用热蒸镀的方法， 用 Cu靶在上述 PET片上蒸镀 1500s, 蒸镀功率 50W， 在光刻胶间隙中得到 3nm厚的 Cu。 用显影液溶解洗去光刻胶， 再用去离子水反复洗涤 3次， 得到含有金属 Cu与石墨烯的透明电极材料。  (4) Evaporation of Cu in the gap of the photoresist: by vapor deposition on the PET sheet by a vapor deposition method for 1500 s, a vapor deposition power of 50 W, and a Cu of 3 nm thick in the gap of the photoresist. The photoresist was washed with a developing solution and washed three times with deionized water to obtain a transparent electrode material containing metal Cu and graphene.
(5 ) 将步骤 （4) 得到的透明电极材料重复前述步骤 （1 ) 和 （2)， 在 Cu透明薄 膜上再制备一层石墨烯薄膜， 得到双层石墨烯的透明电极材料。 透明电极材料的主视图 和左 （右） 视图如图 6中的 A和 B所示。  (5) Repeating the above steps (1) and (2) for the transparent electrode material obtained in the step (4), and further preparing a graphene film on the Cu transparent film to obtain a transparent electrode material of the double-layer graphene. The front view and left (right) view of the transparent electrode material are shown in A and B in Figure 6.
透明电极材料的金属层厚度为 3nm， 金属层层数为 1层； 石墨烯厚度为 1.2nm; 石 墨烯层数为 2层。  The thickness of the metal layer of the transparent electrode material was 3 nm, the number of layers of the metal layer was 1 layer; the thickness of the graphene was 1.2 nm; and the number of layers of the graphene was 2 layers.
透明电极材料的可见光透过率为 70%、 红外光透过率 70%、 方块电阻 0.001Q/sq。 实施例 4 The transparent electrode material has a visible light transmittance of 70%, an infrared light transmittance of 70%, and a sheet resistance of 0.001 Q/sq. Example 4
本实施例是为说明本发明的 a型透明电极材料的制备方法。  This embodiment is a method for preparing a type a transparent electrode material of the present invention.
( 1 ) 石墨烯溶胶的制备： 与实施例 3的步骤 （1 ) 一致， 得到浓度为 10mg/mL的 石墨烯溶胶， 用去离子水稀释， 得到 0.1mg/mL石墨稀溶胶。  (1) Preparation of graphene sol: Consistent with the step (1) of Example 3, a graphene sol having a concentration of 10 mg/mL was obtained, which was diluted with deionized water to obtain a graphite-dilute sol of 0.1 mg/mL.
(2) Ag纳米线与石墨烯混合溶胶的制备： 将单分散 Ag纳米线 （根据文献 Yi Cui 等 Scalable Coating and Properties of Transparent, Flexible, Silver Nanowire Electrodes, ACS NANO,2010,4(5):2955-2963中的方法制备，颗粒粒径 40nm-100nm， 2mg/mL)与步骤（ 1 ) 得到的 O.lmg/mL石墨烯溶胶混合， 体积混合比例 1 : 1。 超声 30min (超声功率 20kW);  (2) Preparation of Ag nanowires and graphene mixed sol: Monodisperse Ag nanowires (according to the literature, Yi Cui et al. Scalable Coating and Properties of Transparent, Flexible, Silver Nanowire Electrodes, ACS NANO, 2010, 4(5): 2955 Prepared by the method of -2963, the particle size of 40 nm - 100 nm, 2 mg / mL) is mixed with the 0.1 mg / mL graphene sol obtained in the step (1), and the volume mixing ratio is 1:1. Ultrasound 30min (ultrasonic power 20kW);
( 3 ) Ag纳米线与石墨烯混合薄膜的制备： 用刮涂的方法将 lmL混合溶胶用玻璃 棒刮涂到 PET (日本艾克 AICA， 型号 HC2106, 大小为 2cmx2cm， 厚度 0.188mm) 上 并晾干， 得到透明电极材料。 透明电极材料的主视图和左（右）视图如图 7中的 A和 B 所示。  (3) Preparation of Ag nanowire and graphene mixed film: 1 mL of mixed sol was scraped with a glass rod to PET (Japan Aike, model HC2106, size 2cmx2cm, thickness 0.188mm) and dried Dry 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 Figure 7.
透明电极材料的金属 Ag与石墨烯混合层厚度为 3nm，金属与石墨烯混合层层数为 The thickness of the mixed layer of metal Ag and graphene of the transparent electrode material is 3 nm, and the number of layers of the mixed layer of metal and graphene is
1层。 1 story.
透明电极材料的可见光透过率为 92%、红外光透过率为 92%、方块电阻为 100Q/sq。 实施例 5  The transparent electrode material had a visible light transmittance of 92%, an infrared light transmittance of 92%, and a sheet resistance of 100 Q/sq. Example 5
本实施例是为说明本发明的 b型透明电极材料的制备方法。  This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
( 1 )制备多孔阳极氧化铝模板:采用两步阳极氧化法 (根据 Hideki Masuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb structures of Anodic Alumina, SCIENCE, 268( 9) 1995 )中提供的方法）制备多孔阳极氧化 铝片， 通过扫描电镜测出该多孔阳极氧化铝片的孔径为 50nm， 孔间距为 150nm;  (1) Preparation of a porous anodized aluminum oxide template: using a two-step anodizing method (according to Hideki Masuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb structures of Anodic Alumina, SCIENCE, 268(9) 1995) The method provided in the method) preparing a porous anodized aluminum sheet, the porous anodized aluminum oxide sheet having a pore diameter of 50 nm and a pore spacing of 150 nm as determined by scanning electron microscopy;
(2) 电子束蒸镀金属层： 用电子束蒸发仪 （Edwars, AUTO 500) 向步骤 （1 ) 得 到的阳极氧化铝片上蒸镀一层金属银， 厚度 20nm;  (2) Electron beam evaporation metal layer: an electron beam evaporator (Edwars, AUTO 500) is used to vaporize a layer of metallic silver on the anodized aluminum sheet obtained in the step (1) to a thickness of 20 nm;
( 3 ) 去除氧化铝模板： 在步骤 （2) 蒸镀有金属银的阳极氧化铝片下方放置石英 片 （锦州华美石英电器厂， 大小为 2Cmx2cm， 厚度为 lmm)， 在浓度为 1%的磷酸溶液 中溶解掉阳极氧化铝， 带孔金属银网格自然沉降到石英片上； 用去离子水洗涤石英片上 多余的磷酸和金属离子， 100°C下干燥 4h; (3) Removal of the alumina template: Place the quartz plate under the anodized aluminum sheet with metal silver vapor deposited in step (2) (Jinzhou Huamei Quartz Electric Factory, size 2 C mx2cm, thickness lmm) at a concentration of 1% The anodized aluminum is dissolved in the phosphoric acid solution, and the porous metal silver mesh is naturally deposited on the quartz plate; the excess phosphoric acid and metal ions on the quartz plate are washed with deionized water, and dried at 100 ° C for 4 h;
(4 ) 制备氧化石墨烯薄膜： 在步骤 （3 ) 得到的有金属网格的石英片上用旋涂仪 以 4000rpm的转速旋涂一层 6nm厚的制备例 1中得到的氧化石墨烯溶胶， 100°C下干燥 lOmin; (4) preparing a graphene oxide film: using a spin coater on a quartz plate having a metal mesh obtained in the step (3) A layer of 6 nm thick graphene oxide sol obtained in Preparation Example 1 was spin-coated at 4000 rpm, and dried at 100 ° C for 10 min;
( 5 ) 热还原氧化石墨烯： 在 Ar气保护下， 将步骤 （4) 得到的含有厚度为 0.8nm 的氧化石墨烯薄膜的石英片放入石英管， 然后将石英管放入管式炉中， 以升温速率每小 时 200°C缓慢升温到 800°C加热 10min， 然后在 Ar气保护下在炉中缓慢冷却至室温， 还 原得到含有石墨烯与金属银的透明电极材料。  (5) Thermal reduction of graphene oxide: Under Ar gas protection, a quartz piece containing a graphene oxide film having a thickness of 0.8 nm obtained in the step (4) is placed in a quartz tube, and then the quartz tube is placed in a tube furnace. The temperature was slowly raised to 800 ° C at a heating rate of 200 ° C per hour for 10 min, and then slowly cooled to room temperature in an oven under the protection of Ar gas to obtain a transparent electrode material containing graphene and metallic silver.
透明电极材料的金属层厚度为 20nm， 金属层层数为 1层； 石墨烯层厚度为 0.8nm， 石墨烯层层数为 1层。  The thickness of the metal layer of the transparent electrode material is 20 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene layer is 0.8 nm, and the number of layers of the graphene layer is 1 layer.
透明电极材料在可见光区透光率为 85%、红外光区透光率为 85%、方块电阻 lQ/sq。 实施例 6  The transparent electrode material has a light transmittance of 85% in the visible light region, a light transmittance of 85% in the infrared light region, and a sheet resistance lQ/sq. Example 6
本实施例是为说明本发明的 b型透明电极材料的制备方法。  This embodiment is a method for preparing a b-type transparent electrode material of the present invention.
( 1 )化学气相沉积的方法制备氮掺杂石墨烯： 用镀膜机（KYUY中科科仪技术发 展有限责任公司， 型号 SBC-2) , 以 M为靶材料， 沉积时间 20s， 在石英片 （锦州华美 石英电器厂， 大小为 2cmx2cm， 厚度为 lmm) 上热蒸镀 50nm厚的 Ni。 将石英片放入 石英管中， 通氢气 （20sccm) 和氩气 （lOOsccm), 当炉体中心温度升高到 800 °C时， 通 入 60sccm的 CH4和 60sccm的 NH3， 将石英管放入炉体中心， lOmin后， 将样品在氢气 流下冷却到室温，得到氮掺杂的石墨烯薄膜，用浓度为 1%的磷酸溶液溶解薄膜上的 Ni， 用去离子水洗涤石墨烯表面三次。 (1) Preparation of nitrogen-doped graphene by chemical vapor deposition: using a coating machine (KYUY Science and Technology Development Co., Ltd., model SBC-2), with M as the target material, deposition time 20s, in quartz plate ( Jinzhou Huamei Quartz Electric Appliance Factory, size 2cmx2cm, thickness lmm) is hot-deposited with 50nm thick Ni. The quartz sheet into a quartz tube, through the hydrogen (of 20 sccm) and argon (lOOsccm), when the furnace temperature is raised to 800 ° C, into the 60sccm of 60sccm of CH 4 and NH 3, the quartz discharge tube After entering the center of the furnace, after lOmin, the sample was cooled to room temperature under a hydrogen stream to obtain a nitrogen-doped graphene film, and the Ni on the film was dissolved in a phosphoric acid solution having a concentration of 1%, and the surface of the graphene was washed three times with deionized water.
(2) 制备聚苯乙烯微球： 在 500mL三口烧瓶中加入 10mL苯乙烯和 150mL水， 通氮气排空气 15min， 恒温水浴 70°C下搅拌 20min， 加入 0.2g过硫酸钾， 70°C下反应 24ho 离心分离得到聚苯乙烯微球单分散水溶液 （苯乙烯微球浓度为 10重量％， 苯乙烯 微球的平均粒径为 1.3μηι)。  (2) Preparation of polystyrene microspheres: Add 10 mL of styrene and 150 mL of water to a 500 mL three-necked 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. A monodisperse aqueous solution of polystyrene microspheres (concentration of styrene microspheres of 10% by weight and average particle diameter of styrene microspheres of 1.3 μm) was obtained by centrifugation at 24 ho.
( 3 ) 以聚苯乙烯微球单层膜为模板制备图案化金属薄膜： 向 4.95mL聚苯乙烯微 球单分散水溶液 （苯乙烯微球浓度为 10重量％) 中加入 0.05mL苯乙烯和 5mL无水乙 醇， 再向该溶液中加入 0.15 L的硫酸（浓度是 98重量％)， 超声 15min， 在容器底部放 入上述步骤 （1 ) 处理的表面有石墨烯薄膜的石英片， 放走容器中的液体， 用去离子水 洗涤三次。用等离子刻蚀（RIE)***（SENTECH, ETCHCAB200), 用氧离子刻蚀 10s， 聚苯乙烯微球粒径减小到 1μηι。 用磁控溅射仪 （ULVAC Inc, ACS-400-C4), 在工作压 强 0.5Pa， 功率 40W条件下， 与石英片垂直溅射 10s， 在聚苯乙烯微球空隙中沉积金属 Al， 得到 lOnm厚的 Al， 孔间距 600nm， 孔径 1μηι。 将前述沉积有金属的石英片浸入甲 苯溶液中溶解模板聚苯乙烯微球后， 并用去离子水洗涤，得到含有金属铝和 Ν掺杂的石 墨烯的透明电极材料。 (3) Preparing a patterned metal film using a polystyrene microsphere monolayer as a template: To a 4.95 mL polystyrene microsphere monodisperse aqueous solution (styrene microsphere concentration of 10% by weight), 0.05 mL of styrene and 5 mL were added. Anhydrous ethanol was added to the solution, and 0.15 L of sulfuric acid (concentration: 98% by weight) was added to the solution, and ultrasonication was carried out for 15 minutes. At the bottom of the container, a quartz sheet having a graphene film treated on the surface of the above step (1) was placed, and the container was discharged. The liquid was 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 the polystyrene microspheres was reduced to 1 μm. Magnetron sputtering (ULVAC Inc, ACS-400-C4), perpendicular to quartz wafers for 10 s at a working pressure of 0.5 Pa and a power of 40 W, depositing metal in the interstices of polystyrene microspheres Al, a lOnm thick Al was obtained, a hole pitch of 600 nm, and a pore diameter of 1 μm. The aforementioned metal-deposited quartz plate was immersed in a toluene solution to dissolve the template polystyrene microspheres, and washed with deionized water to obtain a transparent electrode material containing metal aluminum and cerium-doped graphene.
透明电极材料的金属层厚度为 10nm， 金属层层数为 1层； 石墨烯厚度为 1.2nm， 石墨烯层层数为 1层。  The thickness of the metal layer of the transparent electrode material is 10 nm, and the number of layers of the metal layer is 1 layer; the thickness of the graphene is 1.2 nm, and the number of layers of the graphene layer is 1 layer.
透明电极材料的可见光透过率为 94%、 红外光透过率 94%、 方块电阻 2Q/sq。  The transparent electrode material has a visible light transmittance of 94%, an infrared light transmittance of 94%, and a sheet resistance of 2Q/sq.

Claims

权 利 要 求 Rights request
1、一种透明电极材料， 其特征在于， 该材料包括基片和附着在该基片上的导电层， 该导电层含有石墨烯与金属， 所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述导电层在 可见光区域的透光率为 70-98%， 在红外光区域的透光率为 70-98%。 A transparent electrode material, comprising: a substrate and a conductive layer attached to the substrate, the conductive layer containing graphene and a metal, and the sheet resistance of the conductive layer is ΙΟΟΟΩ/sq or less, 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%.
2、 根据权利要求 1所述的透明电极材料， 其中， 所述导电层由石墨烯与金属的混 合物层形成， 所述石墨烯和金属的重量比为 1 :0.01-10000， 所述石墨烯与金属的混合物 层的层数为 1-20层， 每一层所述石墨烯与金属的混合物层的厚度为 0.2-300nm。 2. The transparent electrode material according to claim 1, wherein the conductive layer is formed of a mixture layer of graphene and a metal, and the weight ratio of the graphene to the metal is 1:0.01 to 10000, and the graphene and the graphene are The number of layers of the metal mixture layer is 1 to 20 layers, and the thickness of the layer of the mixture of the graphene and the metal is 0.2 to 300 nm.
3、 根据权利要求 1所述的透明电极材料， 其中， 所述导电层由石墨烯层和金属层 交替形成， 所述石墨烯层的厚度为 0.2-10nm， 所述石墨烯层的层数为 1-10层， 所述金 属层的厚度为 0.2-300nm， 所述金属层的层数为 1-10层。 The transparent electrode material according to claim 1, wherein the conductive layer is alternately formed of a graphene layer and a metal layer, the graphene layer has a thickness of 0.2 to 10 nm, and the number of layers of the graphene layer is 1-10 layers, the metal layer has a thickness of 0.2-300 nm, and the metal layer has a layer number of 1-10 layers.
4、 根据权利要求 3所述的透明电极材料， 其中， 所述金属层为图案化的金属膜。 The transparent electrode material according to claim 3, wherein the metal layer is a patterned metal film.
5、 根据权利要求 1所述的透明电极材料， 其中， 所述金属为选自银、 铜、 金、 铝、 镍、 铂、 锌、 锡、 铁、 钴、 锰、 钼和钛中的一种或多种。 The transparent electrode material according to claim 1, wherein the metal is one selected from the group consisting of silver, copper, gold, aluminum, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, and titanium. Or a variety.
6、 根据权利要求 1所述的透明电极材料， 其中， 所述基片为在可见光区域的透光 率为 90-100%、 在红外光区域的透光率为 90-100%的玻璃、 石英、 聚乙烯醇膜、 聚酰亚 胺膜、 聚对苯二甲酸乙二酯膜、 聚氯乙烯膜、 聚碳酸酯膜、 聚氨酯膜和聚丙烯酸酯膜中 的一种或多种。 The transparent electrode material according to claim 1, wherein the substrate is glass or quartz having a light transmittance of 90-100% in a visible light region and a light transmittance of 90-100% in an infrared light region. One or more of a polyvinyl alcohol film, a polyimide film, a polyethylene terephthalate film, a polyvinyl chloride film, a polycarbonate film, a polyurethane film, and a polyacrylate film.
7、 一种透明电极材料的制备方法， 其特征在于， 该方法包括， 在基片上形成导电 层， 该导电层含有石墨烯与金属， 所述导电层的方块电阻为 ΙΟΟΟΩ/sq 以下， 所述导电 层在可见光区域的透光率为 70-98%， 在红外光区域的透光率为 70-98%。 A method for preparing a transparent electrode material, comprising: forming a conductive layer on a substrate, the conductive layer containing graphene and a metal, and a sheet resistance of the conductive layer being ΙΟΟΟΩ/sq or less, 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%.
8、 根据权利要求 7所述的方法， 其中， 所述在基片上形成导电层的方法包括， 将 含有石墨烯和金属的分散液附着在基片表面， 在 60-200°C下放置 l-120min后， 冷却至 室温， 然后重复进行 0-19 次以下步骤： 将含有石墨烯和金属的分散液附着在所得到的 石墨烯和金属的混合物层的表面， 在 60-200°C下放置 l-120min， 冷却至室温。 8. The method according to claim 7, wherein the method of forming a conductive layer on the substrate comprises attaching a dispersion containing graphene and a metal to the surface of the substrate, and placing the l- at 60-200 ° C. After 120 minutes, cool to At room temperature, the steps of 0-19 times are repeated: a dispersion containing graphene and a metal is attached to the surface of the obtained layer of the mixture of graphene and metal, placed at 60-200 ° C for l-120 min, and cooled to Room temperature.
9、 根据权利要求 8所述的方法， 其中， 所述含有石墨烯与金属的分散液中的石墨 烯的浓度为 0.001-10mg/mL， 金属的浓度为 0.01-100mg/mL。 The method according to claim 8, wherein the concentration of graphene in the dispersion containing graphene and metal is 0.001-10 mg/mL, and the concentration of metal is 0.01-100 mg/mL.
10、根据权利要求 7-9中任意一项所述的方法， 其中， 每一次含有石墨烯与金属的 分散液的用量为使获得的透明电极材料中每一层所述含有石墨烯与金属的混合物层的 厚度为 0.2-300nm。  The method according to any one of claims 7 to 9, wherein each of the dispersion containing graphene and metal is used in an amount such that each layer of the obtained transparent electrode material contains graphene and metal The thickness of the mixture layer is from 0.2 to 300 nm.
11、 根据权利要求 7所述的方法， 其中， 所述在基片上形成导电层的方法包括， 在基片上交替形成金属层和石墨烯层。  11. The method according to claim 7, wherein the method of forming a conductive layer on a substrate comprises alternately forming a metal layer and a graphene layer on the substrate.
12、 根据权利要求 11所述的方法， 其中， 所述金属层的厚度为 0.2-300nm， 所述 金属层的层数为 1-10层，所述石墨烯层的厚度为 0.2-10tim，所述石墨烯层的层数为 1-10 层。 The method according to claim 11, wherein the metal layer has a thickness of 0.2-300 nm, the metal layer has a layer number of 1-10 layers, and the graphene layer has a thickness of 0.2-10 tim. The number of layers of the graphene layer is 1-10 layers.
13、 根据权利要求 7-9、 11和 12中任意一项所述的方法， 其中， 所述金属为选自 银、 铜、 金、 铝、 镍、 铂、 锌、 锡、 铁、 钴、 锰、 钼和钛中的一种或多种， 所述基片为 在可见光区域的透光率为 90-100%、 在红外光区域的透光率为 90-100%的玻璃、 石英、 聚乙烯醇膜、 聚酰亚胺膜、 聚对苯二甲酸乙二酯膜、 聚氯乙烯膜、 聚碳酸酯膜、 聚氨酯 膜和聚丙烯酸酯膜中的一种或多种。 The method according to any one of claims 7-9, 11 and 12, wherein the metal is selected from the group consisting of silver, copper, gold, aluminum, nickel, platinum, zinc, tin, iron, cobalt, manganese One or more of molybdenum and titanium, the substrate is glass, quartz, polyethylene having a light transmittance of 90-100% in the visible light region and 90-100% transmittance in the infrared light region. One or more of an alcohol film, a polyimide film, a polyethylene terephthalate film, a polyvinyl chloride film, a polycarbonate film, a polyurethane film, and a polyacrylate film.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881841A (en) * 2012-10-16 2013-01-16 北京大学 Semiconductor photoelectric device using copper/graphene composite electrode as anode
CN103906365A (en) * 2014-03-06 2014-07-02 广东工业大学 Manufacturing device for electronic circuit based on graphene and manufacturing method thereof
CN108727068A (en) * 2018-07-03 2018-11-02 句容市博远电子有限公司 A kind of preparation method of thin slice NTC thermistor
WO2022127184A1 (en) * 2020-12-15 2022-06-23 中国华能集团清洁能源技术研究院有限公司 Flexible transparent electrode suitable for flexible photoelectric device, and battery and preparation methods

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US11511999B2 (en) 2017-06-15 2022-11-29 Tata Steel Limited and Centre for Nano Process for producing graphene based transparent conductive electrode and the product thereof
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CN107610814B (en) * 2017-08-30 2020-08-11 中国科学院宁波材料技术与工程研究所 Transparent electrode based on ultrathin metal grid and preparation method thereof
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CN113644143A (en) * 2021-06-25 2021-11-12 惠州学院 Full-transparent photoelectric detector and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008131304A1 (en) * 2007-04-20 2008-10-30 Cambrios Technologies Corporation Composite transparent conductors and methods of forming the same
CN101442105A (en) * 2007-11-21 2009-05-27 中国科学院化学研究所 Organic field effect transistor and special source/drain electrode and preparation method thereof
CN101474899A (en) * 2009-01-16 2009-07-08 南开大学 Grapheme-organic material layered assembling film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008131304A1 (en) * 2007-04-20 2008-10-30 Cambrios Technologies Corporation Composite transparent conductors and methods of forming the same
CN101442105A (en) * 2007-11-21 2009-05-27 中国科学院化学研究所 Organic field effect transistor and special source/drain electrode and preparation method thereof
CN101474899A (en) * 2009-01-16 2009-07-08 南开大学 Grapheme-organic material layered assembling film and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881841A (en) * 2012-10-16 2013-01-16 北京大学 Semiconductor photoelectric device using copper/graphene composite electrode as anode
CN103906365A (en) * 2014-03-06 2014-07-02 广东工业大学 Manufacturing device for electronic circuit based on graphene and manufacturing method thereof
CN108727068A (en) * 2018-07-03 2018-11-02 句容市博远电子有限公司 A kind of preparation method of thin slice NTC thermistor
CN108727068B (en) * 2018-07-03 2021-04-13 句容市博远电子有限公司 Preparation method of thin NTC thermistor
WO2022127184A1 (en) * 2020-12-15 2022-06-23 中国华能集团清洁能源技术研究院有限公司 Flexible transparent electrode suitable for flexible photoelectric device, and battery and preparation methods

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