WO2015100795A1 - 石墨烯复合电极材料的制备方法 - Google Patents

石墨烯复合电极材料的制备方法 Download PDF

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WO2015100795A1
WO2015100795A1 PCT/CN2014/070546 CN2014070546W WO2015100795A1 WO 2015100795 A1 WO2015100795 A1 WO 2015100795A1 CN 2014070546 W CN2014070546 W CN 2014070546W WO 2015100795 A1 WO2015100795 A1 WO 2015100795A1
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glass substrate
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electrode material
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王烨文
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3605—Coatings of the type glass/metal/inorganic compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3634—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing carbon, a carbide or oxycarbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
    • G09G5/00—Control arrangements or circuits for visual indicators common to cathode-ray tube indicators and other visual indicators
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
    • G09G2300/00—Aspects of the constitution of display devices
    • G09G2300/04—Structural and physical details of display devices
    • G09G2300/0421—Structural details of the set of electrodes
    • G09G2300/0426—Layout of electrodes and connections
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material

Definitions

  • the invention relates to a method for preparing a composite electrode material, in particular to a method for preparing a graphene electrode material.
  • a new carbonaceous material, graphene is currently the thinnest but hardest nanomaterial in the world. It is almost completely transparent, absorbing only 2.3% of light, and its resistivity is only about 1 (T 6 Q'cm, better than copper or Silver is lower, which is the material with the lowest resistivity in the world. It can be prepared by chemical vapor deposition (CVD), micromechanical separation, orientation.
  • CVD chemical vapor deposition
  • Graphene has a large specific surface area, high electrical conductivity and high mechanical strength. Based on these properties of graphene, graphene is widely used in the synthesis of nanocomposites, electrical components, and other chemical biosensors. Despite the excellent performance and attractive application prospects of graphene, many factors that restrict the development of graphene still exist. For example, high-purity single-layer graphene is difficult to mass-produce, and graphite oxide obtained by chemical oxidation method Reducing graphene oxide prepared by re-reduction of olefins is difficult to control the degree of reduction of it and the inability to avoid graphitization of graphite oxide in the process of chemical reduction, etc., all of which have the superior performance of graphene, and the same chemistry.
  • the graphene obtained in the vapor deposition method still has a process in which graphene is graphitized. Therefore, how to obtain a high specific surface, the degree of reduction of the graphite woman is the key to the performance of the stone woman. Based on the above problems, graphene is used as an electrode material in the display field, which causes problems such as limited performance of graphene. Summary of the invention
  • the object of the present invention is to provide a method for preparing a graphene composite electrode material, which has a simple process and a long service life of the composite electrode material.
  • the present invention provides a method for preparing a graphene composite electrode material, comprising the following steps:
  • Step 1 providing a glass substrate, the melting point of the glass substrate is greater than 1100;
  • Step 2 after cleaning the glass substrate, forming a metal film on the glass substrate;
  • Step 3 patterning the metal film to form a circuit pattern
  • Step 4 forming a graphite film on the circuit pattern to obtain a graphite composite electrode material Material.
  • the glass substrate is an oxidized group, an alumina-based or a silica-based glass substrate.
  • the total amount of alkali metals in the glass substrate is less than 0.3 ppm, the zirconium content is less than or equal to 0.3 ppm, and the cerium content is less than or equal to 1.4 ppm.
  • the content is less than or equal to (), 6 ppm, the magnesium content is less than (I lppm, the boron content is less than 0.1 ppm, and the copper content is less than (lOlppra, the monument content is less than 0, 2 ppm).
  • the glass substrate has a lithium content of less than or equal to 0.1 ppm, a potassium content of less than 0 ppm, and a sodium content of less than or equal to 0.1 ppm.
  • the metal thin film is formed by sputtering on a glass substrate by a physical vapor deposition process using metal nickel, copper or tantalum as a target.
  • the target purity is greater than 99.9%.
  • the thickness of the metal film is iOnm - 500 nm.
  • the step 3 includes: coating a positive photoresist on the metal film, and after exposing and developing, etching a predetermined pattern with copper acid to form a circuit pattern.
  • the step 4 includes: providing a mask, attaching the mask to the side of the glass substrate on which the circuit pattern is formed, and exposing the circuit pattern, and then forming a graphene film on the circuit pattern.
  • the mask is made of silicon dioxide; the graphene film is formed on the circuit pattern by a chemical vapor deposition process.
  • the invention also provides a method for preparing a graphene composite electrode material, comprising the following steps: Step 1: providing a glass substrate, the melting point of the glass substrate is greater than iiocrc;
  • Step 2 after cleaning the glass substrate, forming a metal film on the glass substrate;
  • Step 3 patterning the metal film to form a circuit pattern
  • Step 4 forming a graphene film on the circuit pattern to obtain a graphene composite electrode material
  • the glass substrate is a cerium oxide-based, alumina-based or silica-based glass substrate; wherein the total amount of alkali metals in the glass substrate is less than 0.3 ppm, the zirconium content is less than or equal to 0.3 ppm, and the titanium content is less than or equal to 1.4ppm, the content of calcium is less than or equal to 0.6ppm, the content of magnesium is less than O. lppm, 4 is less than O. lppm, 4 is less than O.Olppm, and the content of prayer is less than 0.2ppm:
  • lithium content in the glass substrate is less than or equal to O.OOlppm, and the potassium content is less than
  • the uranium content is less than or equal to O.lppm
  • the metal film is formed on the glass substrate by sputtering of a metal nickel, copper or tantalum by a physical vapor deposition process;
  • the metal film has a thickness iOnm - 500 nm.
  • the step 3 includes: coating a positive photoresist on the metal film, and after exposing and developing, etching a predetermined pattern with copper acid to form a circuit pattern.
  • the step 4 includes: providing a mask, attaching the mask to the side of the glass substrate on which the circuit pattern is formed, and exposing the circuit pattern, and then forming a graphene film on the circuit pattern.
  • the mask is made of silicon dioxide; the graphene film is formed on the circuit pattern by a chemical vapor deposition process.
  • the method for preparing a graphene composite electrode material of the present invention directly grows a graphene film on a surface of a circuit pattern through a high temperature resistant glass substrate and a metal catalyst, without transferring, and is not affected by the solvent in the transfer.
  • the film quality is high and no etching is required, and the graphene composite electrode material is directly formed, the process is simple, and since the chemical properties of the graphene are stable, the metal circuit pattern can be protected, and the service life of the graphite composite electrode material is effectively extended. .
  • Figure i is a flow chart of a method for preparing a graphite composite electrode material of the present invention. detailed description
  • the present invention provides a method for preparing a graphene composite electrode material, which comprises the following steps:
  • Step 1 Provide a glass substrate having a melting point greater than 11001:.
  • the glass substrate is selected from a high temperature resistant glass substrate, preferably a glass substrate having a melting point greater than liOOr, wherein the total amount of alkali metals (lithium, potassium, sodium) in the glass substrate is less than 0.3 ppm, the zirconium content is less than or equal to OJppm, and the titanium content is less than or equal to 1.4ppm, the calcium content is less than or equal to 0.6ppm, the magnesium content is less than 0, lppm, the boron content is less than 0.1ppm, the copper content is less than O.Olppm, and the phosphorus content is less than 0.2ppm.
  • the lithium content in the glass substrate is less than or equal to O.OOIppm, potassium containing The amount is less than 0.2 ppm, and the content of #] is less than or equal to 0.1 ppin.
  • the glass substrate is a cerium oxide group, an alumina group or a silica based glass substrate.
  • Step 2 After cleaning the glass substrate, a metal thin film is formed on the glass substrate.
  • the film of the genus is formed of a metal nickel (Ni), copper (Cu) or ruthenium (Ru) as a material, and is formed on a glass substrate by physical vapor deposition (PVD) sputtering.
  • the target purity is greater than 99.9%.
  • the thickness of the metal film iOnm- 500nm consider
  • Step 3 Patterning the metal film to form a circuit pattern.
  • a positive photoresist is coated on the metal thin film, and after exposure and development, a predetermined pattern is etched with copper acid to form a circuit pattern.
  • Step 4 Forming a graphene film on the circuit pattern to obtain a graphene composite electrode material.
  • a mask is provided which is attached to the side of the glass substrate on which the circuit pattern is formed, and the circuit pattern is exposed, and then a graphene film is formed on the circuit pattern.
  • the mask is made of silicon dioxide having a deformation point of 1075 'C and an annealing point of 1180.
  • C the hardening point is 17301: , the maximum continuation temperature ⁇ . C, can be used under 1450 ⁇ in a short time. Since the mask has high temperature resistance, the coefficient of thermal expansion is small, and the shape variable is small at about 1000 ° C, which can effectively ensure the precision of the formation of the graphene film.
  • the graphene film is formed on a circuit pattern by a chemical vapor deposition (CVD) process.
  • the chemical vapor deposition process uses a mixed gas of CH 4 and H 2 /Ar or CH 4 and 3 ⁇ 4, and can have a thickness of 0.35 nm depending on the deposition time in an environment of 600 1050 ° C and 40 Pa - 5 kPa. 50 nm, graphene film with a sheet resistance of 0.1-500 ⁇ / ⁇ .
  • the method for preparing the graphene composite electrode material of the invention directly grows the graphene film on the surface of the circuit pattern through the high temperature resistant glass substrate and the metal catalyst, does not need to be transferred, and is not affected by the solvent in the transfer, and forms a film.
  • the high quality and no etching are required to directly form the graphene composite electrode material, the process is simple, and since the chemical properties of the graphene are stable, the metal circuit pattern can be protected, thereby prolonging the service life of the graphene composite electrode material.

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Abstract

提供一种石墨烯复合电极材料的制备方法，包括以下步骤：步骤1、提供玻璃基板，该玻璃基板的熔点大于1100℃；步骤2、清洗玻璃基板后，在玻璃基板上形成金属薄膜；步骤3、图案化该金属薄膜，以形成电路图形；步骤4、在电路图形上形成石墨烯薄膜，以制得石墨烯复合电极材料。

Description

石 '夏、 的制备方
本发明涉及一种复合电极材料的制备方法， 尤其涉及一种石墨烯 电极材料的制备方法。
Figure imgf000003_0001
碳质新材料， 石墨烯目前是世上最薄却也是最坚硬的纳米材料， 它几乎是 完全透明的， 只吸收 2.3%的光， 而电阻率只约 l(T6 Q'cm , 比铜或银更 低， 为目前世上电阻率最小的材料， 其可以通过化学气相沉积 （Chemical Vapor Deposition, CVD )法, 微机械分离法, 取向附生法等方法制备。
石墨烯具有很大的比表面积、 高导电性及很高的机械强度， 基于石墨 烯的这些性质， 石墨烯被广泛的运用于合成纳米复合材料， 制造电学元 件， 以及其他一些化学生物传感器等。 尽管石墨烯具有十分卓越的性能以 及诱人的应用前景， 但是目前制约石墨烯发展的很多因素也依然存在， 如， 高纯度的单层石墨烯很难大规模生产， 化学氧化法得到的氧化石墨烯 再还原制取的还原氧化石墨烯因难以控制其被还原的程度以及不能避免氧 化石墨在化学还原的过程中再次被石墨化等因素均将石墨烯本来所具有的 优越性能大打折扣， 同样化学气相沉积法中得到的石墨烯依然存在石墨烯 被石墨化的过程。 因此， 怎样得到高比表面， 还原程度较高的石墨婦是石 墨婦发挥其高性能的关键。 基于上述问题， 石墨烯作为电极材料应用于显 示领域， 会产生石墨烯的优越性能受限等问题。 发明内容
本发明的目的在于提供一种石墨烯复合电极材料的制备方法， 其制程 简单， 制得的复合电极材料的使用寿命长。
为实现上述目的， 本发明提供一种石墨烯复合电极材料的制备方法， 包括以下步骤：
步骤 1、 提供玻璃基板， 该玻璃基板的熔点大于 1100 ;
步骤 2、 清洗玻璃基板后， 在玻璃基板上形成金属薄膜；
步骤 3、 图案化该金属薄膜， 以形成电路图形；
步骤 4、 在电路图形上形成石墨婦薄膜， 以制得石墨婦复合电极材 料。
所述玻璃基板为氧化 基、 氧化铝基或二氧化硅基玻璃基板„ 所述玻璃基板中碱金属总量小于 0.3ppm , 锆含量小于或等于 0.3ppm， 钬含量小于或等于 1.4ppm, 4丐含量小于或等于 （),6ppm, 镁含量 小于 （I lppm， 硼含量小于 O. lppm , 铜含量小于 （lOlppra , 碑含量小于 0,2ppm。
所述玻璃基板中锂含量小于或等于 O.OOlppm, 钾含量小于 0„2ppm， 钠含量小于或等于 0。ippm。
所述金属薄膜以金属镍、 铜或钌为靶材， 通过物理气相沉积工艺溅镀 形成于玻璃基板上。
所述靶材纯度大于 99.9%。
所述金属薄膜厚度 iOnm- 500nm。
所述步骤 3 包括： 在金属薄膜上涂布正光阻， 经曝光与显影后， 采用 铜酸蚀刻出预定的图形， 进而形成电路图形。
所述步骤 4 包括： 提供一掩模板， 将该掩模板贴附于玻璃基板的形成 有电路图形侧， 并露出电路图形， 然后在电路图形上形成石墨烯薄膜。
所述掩模板由二氧化硅制成； 所述石墨烯薄膜通过化学气相沉积工艺 形成于电路图形上。
本发明还提供一种石墨烯复合电极材料的制备方法， 包括以下步骤： 步骤 1、 提供玻璃基板， 该玻璃基板的熔点大于 iiocrc ;
步骤 2、 清洗玻璃基板后， 在玻璃基板上形成金属薄膜；
步骤 3、 图案化该金属薄膜， 以形成电路图形；
步骤 4、 在电路图形上形成石墨烯薄膜， 以制得石墨烯复合电极材 料；
其中， 所述玻璃基板为氧化钇基、 氧化铝基或二氧化硅基玻璃基板； 其中， 所述玻璃基板中碱金属总量小于 0.3ppm, 锆含量小于或等于 0.3ppm, 钛含量小于或等于 1.4ppm, 钙含量小于或等于 0.6ppm, 镁含量 小于 O. lppm , 4 舍量小于 O. lppm, 4同含量小于 O.Olppm, ..祷含量小于 0.2ppm:
其中， 所述玻璃基板中锂含量小于或等于 O.OOlppm, 钾含量小于
0.2ppm, 铀含量小于或等于 O.lppm;
其中， 所述金属薄膜以金属镍、 铜或钌为靶材， 通过物理气相沉积工 艺溅镀形成于玻璃基板上；
其中， 所述靶材纯度大于 99.9%。 所述.金属薄膜厚度 iOnm- 500nm。
所述步骤 3 包括： 在金属薄膜上涂布正光阻， 经曝光与显影后， 采用 铜酸蚀刻出预定的图形， 进而形成电路图形。
所述步骤 4 包括： 提供一掩模板， 将该掩模板贴附于玻璃基板的形成 有电路图形侧， 并露出电路图形， 然后在电路图形上形成石墨烯薄膜。
所述掩模板由二氧化硅制成； 所述石墨烯薄膜通过化学气相沉积工艺 形成于电路图形上。
本发明的有益效果： 本发明的石墨烯复合电极材料的制备方法， 通过 耐高温玻璃基板与金属催化剂， 在电路图形表面直接生长石墨烯薄膜， 不 需转移， 不会受转移中溶剂影响， 成膜质量较高且无需蚀刻， 直接形成石 墨烯复合电极材料， 制程简单， 且， 由于石墨烯化学性质很稳定， 可以起 到保护金属电路图形的作用， 进 有效延长石墨婦复合电极材料的使用寿 命。
为了能更进一步了解本发明的特征以及技术内容， 请参阅以下有关本 发明的详细说明与附图， 然而附图仅提供参考与说明用， 并非用来对本发 明加以限制。 附图说明
下面结合附图， 通过对本发明的具体实施方式详细描述， 将使本发明 的技术方案及其它有益效果显而易见。
附图中，
图 i为本发明石墨婦复合电极材料的制备方法的流程图。 具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果， 以下结合本发明 的优选实施例及其附图进行详细描述。
请参阅图 1， 本发明提供一种石墨烯复合电极材料的制备方法， 包括 以下步骤：
步糠 1、 提供玻璃基板， 该玻璃基板的熔点大于 11001：。
所述玻璃基板选用耐高温玻璃基板， 优选熔点大于 liOOr的玻璃基 板， 且该玻璃基板中碱金属（锂、 钾、 钠） 总量小于 0.3ppm， 锆含量小于 或等于 OJppm, 钛含量小于或等于 1.4ppm， 钙含量小于或等于 0.6ppm， 镁含量小于 0, lppm， 硼含量小于 0.1ppm， 铜含量小于 O.Olppm, 磷含量小 于 0.2ppm， 优选的， 所述玻璃基板中锂含量小于或等于 O.OOIppm, 钾含 量小于 0.2ppm， #]含量小于或等于 0.1 ppin。
在本实施例中， 所述玻璃基板为氧化钇基、 氧化铝基或二氧化硅基玻 璃基 。
步骤 2、 清洗玻璃基板后， 在玻璃基板上形成金属薄膜。
所述 1^属薄膜以金属镍（Ni ) 、 铜 （Cu )或钌 （Ru ) 为耙材， 通过物 理气相沉积 ( Physical Vapor Deposition, PVD ) 工艺溅镀形成于玻璃基板 上。 所述靶材纯度大于 99.9%。 所述金属薄膜厚度 iOnm- 500nm„
步骤 3、 图案化该金属薄膜， 以形成电路图形。
具体地， 在金属薄膜上涂布正光阻， 经曝光与显影后， 釆用铜酸蚀刻 出預定的图形， 进而形成电路图形。
步骤 4、 在电路图形上形成石墨烯薄膜， 以制得石墨烯复合电极材 料。
具体地， 提供一掩模板， 将该掩模板贴附于玻璃基板的形成有电路图 形侧， 并露出电路图形， 然后在电路图形上形成石墨烯薄膜。
在本实施例中， 所述掩模板由二氧化硅制成， 其形变点为 1075 'C , 退 火点为 1180。C， 硬化点为 17301： , 最高延续使用温度 誦。 C , 短时间内 可在 1450Γ下运用。 因该掩模板耐高温， 热膨胀率小， 在 1000°C左右形 变量小， 可以有效保证石墨烯薄膜形成的精度。
所述石墨烯薄膜通过化学气相沉积 ( Chemical Vapor Deposition , CVD ) 工艺形成于电路图形上。 具体地， 化学气相沉积工艺中采用 CH4与 H2/Ar或 CH4与 ¾混合气体， 在 600 1050 °C、 40Pa- 5kPa的环境下， 并可根 据沉积时间不同可以得到厚度为 0.35nm- 50nm, 面电阻在 0.1- 500 Ω/口的 石墨烯薄膜。
综上所述， 本发明的石墨烯复合电极材料的制备方法， 通过耐高温玻 璃基板与金属催化剂， 在电路图形表面直接生长石墨烯薄膜， 不需转移， 不会受转移中溶剂影响， 成膜质量较高且无需蚀刻， 直接形成石墨烯复合 电极材料， 制程简单， 且， 由于石墨烯化学性质很稳定， 可以起到保护金 属电路图形的作用， 进而有效延长石墨烯复合电极材料的使用寿命。
以上所述， 对于本领域的普通技术人员来说， 可以根据本发明的技术 方案和技术构思作出其他各种相应的改变和变形， 而所有这些改变和变形 都应属于本发明权利要求的保护范围。

Claims

】、 一种石墨烯复合电极材料的制备方法， 包括以下步骤：
步骤 1、 提供玻璃基板， 该玻璃基板的熔点大于 1100
步骤 2、 清洗玻璃基板后， 在玻璃基板上形成金属薄膜；
步骤 3、 图案化该金属薄膜， 以形成电路图形；
步骤 4、 在电路图形上形成石墨歸薄膜， 以制得石墨歸复合电极材 料。
2、 如权利要求 所述的石墨烯复合电极材料的制备方法， 其中， 所 述玻璃基板为氧化钇基、 氧化铝基或二氧化硅基玻璃基板。
3、 如权利要求 2 所述的石墨婦复合电极材料的制备方法， 其中， 所 述玻璃基板中碱金属总量小于 0.3ppm, 锆含量小于或等于 0.3ppm， 钛含 量小于或等于 1.4ppm, 5'舍量小于或等于 Ο,βρριπ, 4美' f "量小于 O. lppm, 硼含量小于 CUppm， 铜含量小于 0.i)lppm， 磷含量小于 0,2ppm。
4、 如权利要求 3 所述的石墨烯复合电极材料的制备方法， 其中， 所 述玻璃基板中锂含量小于或等于 O.OOlippm, 钾含量小于 0,2ppm， 钠含量 小于或等于 O. lppm.
5、 如权利要求 1 所述的石墨烯复合电极材料的制备方法， 其中， 所 述金属薄膜以金属镍、 铜或钌为靶材， 通过物理气相沉积工艺溅镀形成于 玻璃基板上。
6、 如权利要求 5 所述的石墨婦复合电极材料的制备方法， 其中， 所 述耙材純度大于 99,9%。
7、 如权利要求 1 所述的石墨烯复合电极材料的制备方法， 其中， 所 述金属薄膜厚度 10nm-500nmo
8、 如权利要求 1 所述的石墨烯复合电极材料的制备方法， 其中， 所 述步骤 3 包括： 在金属薄膜上涂布正光阻， 经曝光与显影后， 采用铜酸蚀 刻出预定的图形， 进而形成电路图形。
9、 如权利要求 1 所述的石墨婦复合电极材料的制备方法， 其中， 所 述步骤 4 包括： 提供一掩模板， 将该掩模板贴附于玻璃基板的形成有电路 图形侧， 并露出电路图形， 然后在电路图形上形成石墨烯薄膜。
10、 如权利要求 9所述的石墨烯复合电极材料的制备方法， 其中， 所 述掩模板由二氧化硅制成； 所述石墨烯薄膜通过化学气相沉积工艺形成于 电路图形上。
11、 一种石墨烯复合电极材料的制备方法， 包括以下步骤：
步骤 1、 提供玻璃基板， 该玻璃基板的熔点大于 1100 ;
步骤 2、 清洗玻璃基板后， 在玻璃基板上形成金属薄膜；
步骤 3、 图案化该金属薄膜， 以形成电路图形；
步骤 4、 在电路图形上形成石墨烯薄膜， 以制得石墨烯复合电极材 料；
其中， 所述玻璃基板为氧化钇基、 氧化铝基或二氧化硅基玻璃基板； 其中， 所述玻璃基板中碱金属总量小于 0。3ppm, 锆含量小于或等于 .3ppm, 钛含量小于或等于 L4ppm， 钙含量小于或等于 0.6ppm, 锾含量 小于 （I lppm， 硼含量小于 O. lppm , 铜含量小于 （lOlppra , 碑含量小于
0.2ppm;
其中， 所述玻璃基板中锂含量小于或等于 （XOOlppm, 钾含量小于 0.2ppm, j含量小于或等于 O. lppm;
其中， 所述金属薄膜以金属镍、 铜或钌为靶材， 通过物理气相沉积工 艺溅镀形成于玻璃基板上；
其中， 所述耙材纯度大于 99.9%。
12、 如权利要求 11 所述的石墨烯复合电极材料的制备方法， 其中， 所述金属薄膜厚度 10nm- 500nm。
13、 如权利要求 11 所述的石墨烯复合电极材料的制备方法， 其中， 所述步驟 3 包括： 在金属薄膜上涂布正光阻， 经曝光与显影后， 采用铜酸 蚀刻出預定的图形， 进而形成电路图形。
14、 如权利要求 11 所述的石墨烯复合电极材料的制备方法， 其中， 所述步骤 4 包括： 提供一掩模板， 将该掩模板贴附于玻璃基板的形成有电 路图形侧， 并露出电路图形， 然后在电路图形上形成石墨烯薄膜„
15、 如权利要求 14 所述的石墨烯复合电极材料的制备方法， 其中， 所述掩模板由二氧化硅制成； 所述石墨烯薄膜通过化学气相沉积工艺形成 于电路图形上。
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