WO2015010344A1 - 透明导电层、具有该透明导电层的cf基板及其制备方法 - Google Patents

透明导电层、具有该透明导电层的cf基板及其制备方法 Download PDF

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WO2015010344A1
WO2015010344A1 PCT/CN2013/080438 CN2013080438W WO2015010344A1 WO 2015010344 A1 WO2015010344 A1 WO 2015010344A1 CN 2013080438 W CN2013080438 W CN 2013080438W WO 2015010344 A1 WO2015010344 A1 WO 2015010344A1
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substrate
transparent conductive
conductive layer
transfer medium
layer
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PCT/CN2013/080438
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English (en)
French (fr)
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李冠政
王烨文
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深圳市华星光电技术有限公司
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Priority to US14/111,561 priority Critical patent/US20150029607A1/en
Publication of WO2015010344A1 publication Critical patent/WO2015010344A1/zh
Priority to US14/829,467 priority patent/US9557460B2/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
    • B32B2310/0409—Treatment by energy or chemical effects using liquids, gas or steam using liquids
    • B32B2310/0418—Treatment by energy or chemical effects using liquids, gas or steam using liquids other than water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/22—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials

Definitions

  • Transparent conductive layer Transparent conductive layer, CF substrate having the same, and preparation method thereof
  • the present invention relates to the field of liquid crystal display, and in particular to a graphene transparent conductive layer, a CF substrate having the transparent conductive layer, and a preparation method thereof.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • AZO aluminum-doped zinc oxide
  • ITO transparent conductive material has a light transmittance of 90%, but since the indium element is a rare metal, and the production of the ITO film requires high vacuum and high temperature, the obtained ITO film is relatively brittle. It is not easy to make a flexible electrode, which limits the further development of ITO transparent conductive materials.
  • graphene is a new carbonaceous material in which a single layer of carbon atoms is closely packed into a two-dimensional honeycomb structure.
  • Graphene is currently the thinnest but hardest nanomaterial in the world, and it is almost Fully transparent, it absorbs only 2.3% of light, and its resistivity is only about 1 ( ⁇ 6 ⁇ -cm, lower than copper or silver. It is the world's smallest resistivity material, which can be chemical vapor deposited (Chemical Vapor Deposition). , CVD) method, micro-mechanical separation method, orientation epitaxy method, etc. Since graphene conductivity is comparable to ITO, light transmittance can reach 97%, and the mechanical strength and flexibility of graphene are transparent to ITO.
  • the material is excellent, so graphene can completely replace the ITO to make a transparent conductive electrode or a conductive layer; further, when the graphene is prepared by the CVD method, the production cost is low, high temperature and high pressure are not required, and the obtained graphene is transferred onto the substrate.
  • the process of transparent electrodes or transparent conductive layers has become increasingly mature, and has a broader development prospect in terms of flexible display than ITO transparent conductive materials.
  • Another object of the present invention is to provide a CF substrate having a graphene transparent conductive layer, which uses a graphene transparent conductive layer instead of an ITO transparent conductive layer for CF substrate of a liquid crystal display.
  • the board in order to obtain a graphene transparent conductive layer electrode or an electrostatic derivation layer with high penetration and good flexibility, which is used in a liquid crystal display panel, the transmittance of the liquid crystal panel can be enhanced, and the use of the backlight can be reduced.
  • Another object of the present invention is to provide a method for preparing a CF substrate having a graphene transparent conductive layer, which is simple in operation and easy to realize in process conditions, and has a CF substrate having a graphene transparent conductive layer and has high penetration.
  • the advantage of good flexibility is to provide a method for preparing a CF substrate having a graphene transparent conductive layer, which is simple in operation and easy to realize in process conditions, and has a CF substrate having a graphene transparent conductive layer and has high penetration.
  • the present invention provides a transparent conductive layer made of a graphene transparent conductive material, which is in the form of a film having a thickness of 0.36 nm to 10 nm, a visible light transmittance of 80-97%, and a sheet resistance of 30. -500 ⁇ / port.
  • the present invention also provides a CF substrate, comprising: a CF substrate body and a transparent conductive layer formed on the CF substrate body, wherein the transparent conductive layer is made of a graphene transparent conductive material and has a film shape with a thickness of 0.36 nm. -10 nm, the visible light transmittance is 80-97%, and the sheet resistance is 30-500 ⁇ / ⁇ .
  • the CF substrate body includes a glass substrate and a color resist layer formed on the glass substrate.
  • the color resist layer includes a plurality of pixel units arranged in an array and a black matrix located at a periphery of the pixel units.
  • the transparent conductive layer is located on the color resist layer.
  • the transparent conductive layer and the color resist layer are respectively located on both sides of the glass substrate.
  • the invention also provides a method for preparing a CF substrate, comprising the following steps:
  • Step 11 The growth substrate is placed in a chemical vapor deposition reactor, and a mixed gas of a carbon source gas and a carrier gas is introduced, and the reaction is carried out at 900-1120 ° C: 40 Pa-5000 KPa for 1 to 60 min. Forming a graphene film on the substrate, the graphene film having a thickness of 0.36 nm to 10 nm, a visible light region transmittance of 80-97%, and a sheet resistance of 30-500 ⁇ / ⁇ ;
  • Step 12 coating a transfer medium layer on the graphene film to obtain a transfer medium layer/graphene film/growth substrate combination
  • Step 13 immersing the transfer medium layer/graphene film/growth substrate assembly in a growth substrate etching solution, removing the growth substrate, and obtaining a transfer medium layer/graphene film combination;
  • Step 14 providing a CF substrate body, the CF substrate body comprising a glass substrate and a color resist layer formed on the glass substrate;
  • Step 15 The transfer medium layer/graphene film combination body is placed on the CF substrate body and transferred at room temperature to obtain a transfer medium layer/graphene film/CF substrate body combination body;
  • Step 16 The transfer medium layer/graphene film/CF substrate body assembly is placed in a transfer medium layer removal solvent to remove the transfer medium layer, and a graphene film is formed on the CF substrate body, that is, on the CF substrate body. A transparent conductive layer is formed.
  • the transfer medium layer/graphene film combination is placed on the CF substrate On the color resist layer of the body; in the step 16, the transparent conductive layer is formed on the color resist layer of the CF substrate body.
  • the transfer medium layer/graphene film combination is placed on the glass substrate of the CF substrate body; in the step 16, the transparent conductive layer is formed on the glass substrate of the CF substrate body.
  • the carbon source gas is methane, ethylene, or acetylene;
  • the carrier gas is hydrogen or a mixed gas of hydrogen and argon;
  • the growth substrate is a metal foil prepared by Ni, Cu or Ru; It is a FeCl 3 solution or an acid solution;
  • the transfer medium layer is polymethyl methacrylate or polydimethyl acrylamide.
  • the carbon source gas is methane; the carrier gas is hydrogen; the growth substrate is Cu foil, the purity of the copper foil is >99%; the transfer medium layer is polymethyl methacrylate;
  • the substrate etching solution is a 0.1-1.5 mol/LFeCl 3 solution; and the transfer medium layer removing solvent is an acetone alcohol solution.
  • the transparent conductive layer made of graphene of the present invention has a conductivity comparable to that of a transparent conductive layer made of ITO, and the transparent conductive layer made of graphene has a light transmittance of 97. %, and the transparent conductive layer made of graphene of the present invention is superior in mechanical strength and flexibility to a transparent conductive layer made of ITO, and is more suitable for use in a flexible substrate such as an organic light emitting diode substrate, and using a CVD method.
  • the graphene transparent conductive layer is prepared, the operation is simple, the process conditions are easy to realize, and the cost is lower.
  • the graphene transparent conductive layer is applied to the liquid crystal display panel, the transmittance of the liquid crystal panel can be enhanced, and the use of the backlight can be reduced; and the CF substrate having the graphene transparent conductive layer of the present invention can be prepared.
  • the graphene film is formed on the growth substrate by the CVD method, and then transferred onto the CF substrate body, which is simple in process and low in cost.
  • 1 is a schematic structural view of a transparent conductive layer of the present invention
  • 2 is a flow chart of a method for preparing a transparent conductive layer of the present invention
  • FIG. 3 is a schematic structural view of a first preferred embodiment of a CF substrate of the present invention.
  • FIG. 4 is a schematic structural view of a second preferred embodiment of a CF substrate according to the present invention.
  • Fig. 5 is a flow chart showing a method of preparing a CF substrate of the present invention. detailed description
  • the present invention provides a transparent conductive layer 20 made of a graphene transparent conductive material, which is in the form of a film having a thickness of 0.36 nm to 10 nm and a visible light transmittance of 80 to 97%.
  • the sheet resistance is 30-500 ⁇ / ⁇ .
  • the transparent conductive layer 20 has good electrical conductivity and light transmission property, and can completely replace the existing transparent conductive layer made of indium tin oxide (ITO) for touch screen, liquid crystal display, organic photovoltaic cell, organic light emitting diode and the like.
  • ITO indium tin oxide
  • the transparent conductive layer 20 made of graphene is superior in mechanical strength and flexibility, and is more suitable for use in the field of flexible substrates.
  • the transparent conductive layer 20 is prepared by using a chemical vapor deposition method.
  • the operation is simple, the process conditions are easy to implement, and the cost is lower.
  • the method for preparing the transparent conductive layer 20 includes the following steps:
  • Step 1 The growth substrate is placed in a chemical vapor deposition reactor, and a mixed gas of a carbon source gas and a carrier gas is introduced, and the reaction is carried out at 900-1120 ° C:, 40 Pa-5000 KPa for 1 to 60 min, and is grown. A graphene film is formed on the substrate.
  • the growth substrate is made of nickel (Ni), copper (Cu) or ruthenium (Ru), preferably a metal foil prepared by Ni, Cu or Ru.
  • the carbon source gas and the carrier gas are different depending on the growth substrate material.
  • the growth substrate is a Cu foil, and the purity of the copper foil is >99%.
  • the carbon source gas is mainly a hydrocarbon, and the carbon source determines a growth temperature of the chemical vapor deposition method.
  • the carbon source gas is preferably methane, ethylene, or acetylene.
  • the carbon source gas is the carrier gas. It is hydrogen or a mixed gas of hydrogen and argon.
  • the carrier gas is hydrogen.
  • the carbon source gas is pyrolyzed to grow graphene on the surface of the growth substrate.
  • a metal growth substrate having a relatively high carbon content such as Ni
  • the carbon atoms generated by the carbon source during the cracking penetrate into the metal growth substrate at a high temperature, and are cooled. At the same time, nucleation is precipitated from the inside, and then a graphene film is produced.
  • a metal growth substrate having a lower carbon content such as Cu carbon atoms generated by cracking of the gaseous carbon source at a high temperature are adsorbed on the metal surface, and then nucleated and grown.
  • "graphene island” and through “stone The two-dimensional growth of Moen Island combines to obtain a continuous graphene film. When prepared by CVD, the formed graphene film is of high quality and can achieve large-area growth.
  • Step 2 coating a transfer medium layer on the graphene film to obtain a transfer medium layer/graphene film/growth substrate combination.
  • the transfer medium layer is polymethyl methacrylate (PMMA) or polydimethyl acrylamide
  • the transfer medium layer is polymethyl methacrylate.
  • the macroscopic strength is low, and the transfer process is extremely easy to break.
  • the use of the transfer medium can ensure that the graphene film has a complete structure and no damage after transfer; and has no graphene film. Pollution.
  • Step 3 The transfer medium layer/graphene film/growth substrate assembly is immersed in a growth substrate etching solution, and the growth substrate is removed to obtain a transfer medium layer/graphene film combination.
  • the growth substrate etching liquid varies depending on the growth substrate, and is usually a FeCl 3 solution (corrosion Cu growth substrate, etc.), an acid solution (corrosion Ni growth substrate, etc.), etc.; in the present embodiment, the growth substrate etching solution is 0.1-1.5 mol/L FeCl 3 solution; it can corrode copper foil to separate the graphene film from the growth substrate.
  • Step 4 The transfer medium layer/graphene film combination is placed on a substrate and transferred at room temperature to obtain a transfer medium layer/graphene film/substrate combination.
  • the substrate may be a CF substrate body, a glass substrate, a plastic substrate or the like to be provided with a conductive electrode or a conductive layer; it may be selected as needed.
  • Step 5 The transfer medium layer/graphene film/substrate combination is placed in a transfer medium layer to remove the solvent, and the transfer medium layer is removed, that is, the transparent conductive layer 20 is obtained on the substrate.
  • the transfer medium layer removing solvent is a solvent capable of removing the transfer medium layer without damaging and contaminating the graphene film, which can be appropriately selected depending on the properties of the graphene and the transfer medium layer itself. Since the acetone alcohol solution can effectively remove polymethyl methacrylate, it does not affect the graphene solution.
  • the transparent conductive layer 20 is applied to a CF substrate of a liquid crystal display panel as an electrode, and a CF substrate having a graphene transparent conductive material of the present invention is obtained as a first preferred embodiment of the present invention. 40.
  • the transparent conductive layer 20 is formed on the CF substrate body 40.
  • the transparent conductive layer 20 is made of a graphene transparent conductive material and has a film shape with a thickness of 0.36 nm to 10 nm and a visible light transmittance of 80. -97%, surface resistance is 30-500 ⁇ / port.
  • the CF substrate body 40 includes a glass substrate 42 and a color resist layer 44 formed on the glass substrate 42.
  • the glass substrate 42 is a high-purity alkali-free glass, and the color resist layer 44 includes an array of numbers. Pixel units and black matrices located at the periphery of the pixel units.
  • the transparent conductive layer 20 is formed on the color resist layer 44 as a common electrode of the liquid crystal display panel, and forms an electric field with a pixel electrode (not shown) on the TFT substrate (not shown).
  • the CF substrate is usually a CF substrate in a high definition display mode; however, it is not limited thereto, and may be a CF substrate in another display mode in which a transparent conductive electrode is required.
  • FIG. 4 is a schematic structural view of a second preferred embodiment of the CF substrate of the present invention.
  • the transparent conductive layer 20 and the color resist layer 44 are respectively formed on two sides of the glass substrate 42.
  • the layer 20 serves as an electrostatic derivation layer to guide the static electricity in the liquid crystal display panel, thereby prolonging the service life of the liquid crystal display panel.
  • a protective film is applied on the surface of the ITO to protect the ITO electrostatic discharge layer, and the electrostatic discharge layer prepared by using the graphene transparent conductive layer 20 in the present invention does not need to be protected. Layer, reducing production costs.
  • the CF substrate is usually a CF substrate in an In-Plane Switching (IPS) display mode or a CF in a Fringe Field Switching (FSS) display mode. Substrate. However, it is not limited to the CF substrate in the two display modes, and may be a CF substrate in another display mode in which an electrostatic discharge layer is to be attached.
  • IPS In-Plane Switching
  • FSS Fringe Field Switching
  • the present invention also provides a method for preparing a CF substrate, comprising the following steps:
  • Step 11 The growth substrate is placed in a chemical vapor deposition reactor, and a mixed gas of a carbon source gas and a carrier gas is introduced, and the reaction is carried out at 900-1120 ° C: 40 Pa-5000 KPa for 1 to 60 min.
  • a graphene film is formed on the substrate, and the graphene film has a thickness of 0.36 nm to 10 nm, a visible light region transmittance of 80 to 97%, and a sheet resistance of 30 to 500 ⁇ / ⁇ .
  • the growth substrate is made of nickel (Ni), copper (Cu) or ruthenium (Ru), preferably Ni,
  • the metal foil prepared by Cu or Ru differs in the growth substrate material, and the carbon source gas and the carrier gas are different.
  • the growth substrate is a Cu foil, and the purity of the copper foil is > 99%.
  • the carbon source gas is mainly a hydrocarbon, and the carbon source determines the growth temperature of the chemical vapor deposition method.
  • the carbon source gas is preferably methane, ethylene, or acetylene.
  • the carbon source gas is a pit.
  • the carrier gas is hydrogen or a mixed gas of hydrogen and argon.
  • the carrier gas is hydrogen.
  • the graphene is grown by pyrolysis of the carbon source gas on the surface of the growth substrate.
  • the carbon source generated by the carbon source during the cracking is oozing at a high temperature.
  • nucleation is precipitated from the inside of the metal growth substrate to form a graphene film;
  • carbon atoms produced by cracking of the gaseous carbon source at a high temperature are adsorbed to The metal surface, and then nucleation, grows into a "graphene island", and a two-dimensional growth of "graphene island” is combined to obtain a continuous graphene film.
  • the formed graphene film is high in quality and can realize large-area growth.
  • Step 12 Coating the transfer medium layer on the graphene film to obtain a transfer medium layer/graphene film/growth substrate combination.
  • the transfer medium layer is polymethyl methacrylate or polydimethyl acrylamide.
  • the transfer medium layer is polymethyl methacrylate.
  • the macroscopic strength is low, and the transfer process is extremely easy to break.
  • the use of the transfer medium can ensure that the graphene film has a complete structure and no damage after transfer; and has no graphene film. Pollution.
  • Step 13 The transfer medium layer/graphene film/growth substrate assembly is immersed in a growth substrate etching solution, and the growth substrate is removed to obtain a transfer medium layer/graphene film combination.
  • the growth substrate etching liquid varies depending on the growth substrate, and is usually a FeCl 3 solution (corrosion Cu growth substrate, etc.), an acid solution (corrosion Ni growth substrate, etc.), etc.; in the present embodiment, the growth substrate etching solution is 0.1-1.5 mol/L FeCl 3 solution; it can corrode copper foil to separate the graphene film from the growth substrate.
  • Step 14 A CF substrate body 40 is provided.
  • the CF substrate body 40 includes a glass substrate 42 and a color resist layer 44 formed on the glass substrate 42.
  • the color resist layer 44 is formed on one side of the glass substrate by a yellow light process such as cleaning, coating, prebaking, exposure, development, post-baking, etc., and the color resist layer 44 includes a plurality of pixel units arranged in an array. And a black matrix located at the periphery of the pixel units.
  • Step 15 The transfer medium layer/graphene film combination body is placed on the CF substrate body 40, and transferred at room temperature to obtain a transfer medium layer/graphene film/CF substrate body assembly.
  • the transfer medium layer/graphene film combination can be placed in the color of the CF substrate body 40.
  • the resist layer 44 (shown in FIG. 3) serves as a common electrode of the liquid crystal display panel; the transfer medium layer/graphene film combination body may also be placed on the glass substrate 42 of the CF substrate body 40 (as shown in FIG. 4). Show) as an electrostatic derivation layer.
  • Step 16 The transfer medium layer/graphene film/CF substrate body assembly is placed in a transfer medium layer removal solvent to be cleaned, the transfer medium layer is removed, and a graphene film is formed on the CF substrate body 40, that is, on the CF substrate body.
  • a transparent conductive layer 20 is formed on 40.
  • the transfer medium layer removes the solvent to remove the transfer medium layer and does not damage and contaminate the graphite
  • the solvent of the olefinic film can be reasonably selected according to the properties of the graphene and the material of the transfer medium layer itself. Since the acetone alcohol solution can effectively remove polymethyl methacrylate, it does not affect the graphene solution.
  • the transparent conductive layer 20 is formed on the color resist layer 44, and serves as a common electrode of the liquid crystal display panel and a pixel electrode on the TFT substrate (not shown). (not shown) an electric field is formed to drive the liquid crystal molecules to rotate; at this time, the CF substrate is generally a CF substrate in a high definition display mode; however, it is not limited thereto, and may be other display modes in which a transparent conductive electrode is required to be disposed.
  • the CF substrate is generally a CF substrate in a high definition display mode; however, it is not limited thereto, and may be other display modes in which a transparent conductive electrode is required to be disposed.
  • the transparent conductive layer 20 functions as an electrostatic discharge layer to guide the static electricity in the liquid crystal display panel and prolong the service life of the liquid crystal display panel.
  • the ruthenium layer is used as the electrostatic discharge layer, a protective film is applied on the surface of the ruthenium to protect the ruthenium-derived electrostatically-derived layer, and the electrostatic-derived layer obtained by using the graphene transparent conductive layer 20 in the present invention does not need to be protected. Layer, reducing production costs.
  • the CF substrate is usually a CF substrate in an In-Plane Switching (IPS) display mode or a CF in a Fringe Field Switching (FSS) display mode. Substrate. However, it is not limited to the CF substrate in the two display modes, and may be a CF substrate in another display mode in which an electrostatic discharge layer is to be attached.
  • IPS In-Plane Switching
  • FSS Fringe Field Switching
  • the transparent conductive layer made of graphene of the present invention has a conductivity comparable to that of a transparent conductive layer made of ITO, and the transparent conductive layer made of graphene has a light transmittance of 97%.
  • the transparent conductive layer made of graphene of the present invention is superior in mechanical strength and flexibility to a transparent conductive layer made of ITO, and is more suitable for use in a flexible substrate such as an organic light emitting diode substrate, and is prepared by a CVD method.
  • the graphene transparent conductive layer is used, the operation is simple, the process conditions are easy to realize, and the cost is lower.
  • the graphene transparent conductive layer is applied to the liquid crystal display panel, the transmittance of the liquid crystal panel can be enhanced, and the use of the backlight can be reduced; and the method for preparing the CF substrate having the graphene transparent conductive layer of the present invention
  • the graphene film is formed on the growth substrate by the CVD method, and then transferred onto the CF substrate body, which is simple in process and low in cost.

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Abstract

本发明提供一种透明导电层、具有该透明导电层的CF基板及其制备方法，所述透明导电层由石墨烯透明导电材料制成，呈薄膜状，其厚度为0.36nm-10nm，可见光区穿透率为80-97%，面电阻为30-500Ω/口；可以代替现有的ITO透明导电层，且机械强度和柔韧性更好。具有石墨烯透明导电层的CF基板，利用石墨烯透明导电层代替ITO透明导电层应用于CF基板中，以得到穿透高、柔韧性良好的电极或静电导出层，其应用于液晶显示面板中，可以增强液晶面板的穿透率，减少背光的使用。所述具有石墨烯透明导电层的CF基板的制备方法采用CVD法将石墨烯形成在生长基板上，然后转印至CF基板本体上，工艺简单，成本较低。

Description

透明导电层、 具有该透明导电层的 CF基板及其制备方法
技术领域
本发明涉及液晶显示领域， 特别涉及一种石墨烯透明导电层、 具有该 透明导电层的 CF基板及其制备方法。 背景技术
目前， 普遍使用的透明导电材料为混合金属氧化物透明导电材料， 例 如氧化铟锡（ITO ) 、 氧化铟锌（IZO ) 、 铝掺杂氧化锌（AZO ) 。 其中用 得最多的是 ITO透明导电材料， 其透光率达到 90%, 但由于其中铟元素是 稀贵金属， 且 ITO薄膜的生产需要高真空度及较高温度， 同时获得的 ITO 薄膜较脆， 不易制成柔性电极， 限制了 ITO透明导电材料的进一步发展。
近年来， 研究发现， 石墨烯 （graphene )是一种单层碳原子紧密堆积 成二维蜂窝状结构的碳质新材料， 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 1(Τ6 Ω-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。 由于石墨烯导电率可与 ITO媲美， 透光率可达 97%, 且石 墨烯的机械强度和柔韧性都比 ITO透明导电材料优良， 故而石墨烯完全可 以替代 ITO制作透明导电电极或导电层； 进一步的， CVD法制备石墨烯时 生产成本低， 不需要高温、 高压， 且所制得的石墨烯转印至基板上做透明 电极或透明导电层的工艺已经日趋成熟， 在柔性显示上相对 ITO透明导电 材料来说具有更广阔的发展前景。
由此可见， 有必要制备一种各项参数合适的石墨烯透明导电层， 代替 ITO 透明导电层应用于液晶显示器的 CF基板中， 以得到穿透高、 柔韧性 良好的石墨烯透明导电层电极， 可以对应增强使用所述石墨烯透明导电材 料的 CF基板的液晶显示面板的穿透率， 减少背光的使用。 发明内容
本发明的目的在于提供一种石墨烯透明导电层， 可以代替现有的混合 金属氧化物透明导电层， 且机械强度和柔韧性更好。
本发明的另一目的在于提供一种具有石墨烯透明导电层的 CF基板， 其使用石墨烯透明导电层代替 ITO透明导电层应用于液晶显示器的 CF基 板中， 以得到穿透高、 柔韧性良好的石墨烯透明导电层电极或静电导出 层， 使其用于液晶显示面板中， 可以增强液晶面板的穿透率， 减少背光的 使用。
本发明的又一目的在于提供一种具有石墨烯透明导电层的 CF基板的 制备方法， 操作简单， 工艺条件容易实现， 所制得的具有石墨烯透明导电 层的 CF基板， 具有穿透高、 柔韧性良好的优势。
为实现上述目的， 本发明提供一种透明导电层， 由石墨烯透明导电材 料制成， 呈薄膜状， 其厚度为 0.36nm-10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500Ω/口。
本发明还提供一种 CF基板， 包括： CF基板本体、 及形成于 CF基板 本体上的透明导电层， 所述透明导电层由石墨烯透明导电材料制成， 呈薄 膜状， 其厚度为 0.36nm-10nm, 可见光区穿透率为 80-97%, 面电阻为 30- 500Ω/Ο。
所述 CF基板本体包括玻璃基板及形成于玻璃基板上的色阻层， 该色 阻层包括阵列排布的数个像素单元及位于该些像素单元外围的黑色矩阵。
所述透明导电层位于所述色阻层上。
所述透明导电层与色阻层分别位于玻璃基板的两侧。
本发明还提供一种 CF基板的制备方法， 包括如下步骤：
步骤 11、 将生长基板置于化学气相沉积法反应器内， 通入碳源气体和 载气气体的混合气体， 在 900-1120 °C：、 40Pa-5000KPa 的条件下反应 1- 60min, 在生长基板上形成石墨烯薄膜， 所述石墨烯薄膜厚度为 0.36nm- 10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500Ω/口；
步骤 12、 在石墨烯薄膜上涂布转移介质层， 得到转移介质层 /石墨烯 薄膜 /生长基板结合体；
步骤 13、 将所述转移介质层 /石墨烯薄膜 /生长基板结合体浸渍于生长 基板腐蚀液中， 除去生长基板， 得到转移介质层 /石墨烯薄膜结合体；
步骤 14、 提供 CF基板本体， 所述 CF基板本体包括玻璃基板及形成 于玻璃基板上的色阻层；
步骤 15、 将所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体上， 在室温下转印， 得到转移介质层 /石墨烯薄膜 /CF基板本体结合体；
步骤 16、 将所述转移介质层 /石墨烯薄膜 /CF基板本体结合体放入转移 介质层去除溶剂中清洗， 除去转移介质层， 在 CF基板本体上形成石墨烯 薄膜， 即在 CF基板本体上形成透明导电层。
所述步骤 15 中， 所述转移介质层 /石墨烯薄膜结合体置于 CF基板本 体的色阻层上； 所述步骤 16中， 透明导电层形成于所述 CF基板本体的色 阻层上。
所述步骤 15 中， 所述转移介质层 /石墨烯薄膜结合体置于 CF基板本 体的玻璃基板上； 所述步骤 16中， 透明导电层形成于所述 CF基板本体的 玻璃基板上。
所述碳源气体为甲烷、 乙烯、 或乙炔； 所述载气气体为氢气或氢气与 氩气的混合气体； 所述生长基板为 Ni、 Cu或 Ru制备的金属箔； 所述生长基 板腐蚀液为 FeCl3溶液或酸溶液； 所述转移介质层为聚甲基丙烯酸甲酯或聚 二甲基丙烯酰胺。
所述碳源气体为甲烷； 所述载气气体为氢气； 所述生长基板为 Cu箔， 所述铜箔的纯度> 99%； 所述转移介质层为聚甲基丙烯酸甲酯； 所述生长 基板腐蚀液为 0.1-1.5mol/LFeCl3溶液； 所述转移介质层去除溶剂为丙酮酒 精溶液。
本发明的有益效果： 本发明的由石墨烯制成的透明导电层， 导电率可 与由 ITO制成的透明导电层相媲美， 由石墨烯制成的透明导电层的透光率 可达 97%, 且本发明的由石墨烯制成的透明导电层的机械强度和柔韧性都 比由 ITO制成的透明导电层优良， 更适合应用于有机发光二极管基板等柔 性基板领域， 且使用 CVD 法制备石墨烯透明导电层时， 操作简单， 工艺 条件容易实现， 故而成本更低。 将所述石墨烯透明导电层应用于液晶显示 领域， 制得具有石墨烯透明导电层的 CF基板， 由于使用透光性能、 机械 强度和柔韧性更好的石墨烯透明导电层代替 ITO透明导电层， 因此该具有 石墨烯透明导电层的 CF基板应用于液晶显示面板中， 可以增强液晶面板 的穿透率， 减少背光的使用； 且本发明所述具有石墨烯透明导电层的 CF 基板的制备方法采用 CVD 法将石墨烯薄膜形成在生长基板上， 然后转印 至 CF基板本体上， 工艺简单， 成本较低。
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 1为本发明透明导电层的结构示意图； 图 2为本发明透明导电层的制备方法流程图；
图 3为本发明 CF基板第一优选实施例的结构示意图；
图 4为本发明 CF基板第二优选实施例的结构示意图；
图 5为本发明 CF基板的制备方法流程图。 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及图 2 , 本发明提供一种透明导电层 20, 由石墨烯透明导 电材料制成， 呈薄膜状， 其厚度为 0.36nm-10nm, 可见光区穿透率为 80- 97%, 面电阻为 30-500Ω/口。 该透明导电层 20 具有良好的导电性能和透 光性能， 完全可以代替现有的由氧化铟锡（ITO ) 制成的透明导电层应用 于触摸屏、 液晶显示、 有机光伏电池、 有机发光二极管等领域， 且， 由石 墨烯制成的透明导电层 20 的机械强度和柔韧性更优， 更适合应用于柔性 基板领域。
所述透明导电层 20使用化学气相沉积法制备， 操作简单， 工艺条件 容易实现， 成本更低， 具体的， 请参阅图 2, 所述透明导电层 20的制备方 法， 包括如下步骤：
步骤 1 , 将生长基板置于化学气相沉积法反应器内， 通入碳源气体和 载气气体的混合气体， 在 900-1120 °C：、 40Pa-5000KPa 的条件下反应 1- 60min, 在生长基板上形成石墨烯薄膜。
所述生长基板由镍（Ni ) 、 铜 （Cu )或 4了 （Ru )制得， 优选为 Ni、 Cu或 Ru制备的金属箔， 生长基板材料不同则碳源气体和载气气体有所不 同， 本实施例中生长基板为 Cu箔， 且所述铜箔的纯度 > 99%。
所述碳源气体主要为烃类， 碳源决定化学气相沉积法的生长温度， 本 方法中碳源气体优选甲烷、 乙烯、 或乙炔， 在本实施例中碳源气体为甲 所述载气气体为氢气或氢气与氩气的混合气体， 在本实施例中所述载 气气体为氢气。
通过所述碳源气体在生长基板表面高温分解生长石墨烯， 对于 Ni等 具有较高溶碳量的金属生长基板， 碳源在裂解时产生的碳原子在高温时渗 入金属生长基板内， 在降温时再从其内部析出成核， 进而生产成石墨烯薄 膜； 对于 Cu等具有较低溶碳量的金属生长基板， 高温下气态碳源裂解生 产的碳原子吸附于金属表面， 进而成核生长成 "石墨烯岛" ， 并通过 "石 墨烯岛" 的二维长大合并得到连续的石墨烯薄膜。 CVD法制备时， 所形成 的石墨烯薄膜质量很高， 且可实现大面积生长。
步骤 2, 在石墨烯薄膜上涂布转移介质层， 得到转移介质层 /石墨烯薄 膜 /生长基板结合体。
所述转移介质层为聚甲基丙烯酸甲酯 （PMMA )或聚二甲基丙烯酰胺
( PDMA ) 。 在本实施例中所述转移介质层为聚甲基丙烯酸甲酯。
对于仅有数纳米厚度的石墨烯薄膜而言， 其宏观强度低， 转移过程极 易破损， 所述转移介质的使用， 能够保证石墨烯薄膜在转移后结构完整、 无破损； 且对石墨烯薄膜无污染。
步骤 3 , 将所述转移介质层 /石墨烯薄膜 /生长基板结合体浸渍于生长基 板腐蚀液中， 除去生长基板， 得到转移介质层 /石墨烯薄膜结合体。
生长基板腐蚀液视生长基板的不同而有所不同， 通常为 FeCl3溶液（腐 蚀 Cu生长基板等） 、 酸溶液（腐蚀 Ni生长基板等）等； 在本实施例中所述 生长基板腐蚀液为 0.1-1.5mol/L的 FeCl3溶液； 其能够腐蚀铜箔， 实现石墨 烯薄膜与生长基板的分离。
步骤 4, 将所述转移介质层 /石墨烯薄膜结合体置于基片上， 在室温下 转印， 得到转移介质层 /石墨烯薄膜 /基片结合体。
所述基片可以是待设置导电电极或导电层的 CF基板本体、 玻璃基 板、 塑料基板等； 其可根据需要进行选择。
步骤 5 , 将所述转移介质层 /石墨烯薄膜 /基片结合体放入转移介质层去 除溶剂中清洗， 除去转移介质层， 即在基片上得到透明导电层 20。
所述转移介质层去除溶剂为能够除去转移介质层且不伤害和污染石墨 烯薄膜的溶剂， 其可根据石墨烯和转移介质层自身材料的性质进行合理选 择。 由于丙酮酒精溶液能够有效清除聚甲基丙烯酸甲酯， 且不会对石墨烯 精溶液。
请参阅图 3 , 将所述透明导电层 20 应用于液晶显示面板的 CF基板 中， 作为电极， 得到本发明使用石墨烯透明导电材料的 CF基板第一优选 实施例， 其具体包括： CF基板本体 40、 及形成于 CF基板本体 40上的透 明导电层 20 , 所述透明导电层 20 由石墨烯透明导电材料制成， 呈薄膜 状， 其厚度为 0.36nm-10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500 Ω/口。
所述 CF基板本体 40包括玻璃基板 42及形成于玻璃基板 42上的色阻 层 44, 所述玻璃基板 42为高纯无碱玻璃， 该色阻层 44包括阵列排布的数 个像素单元及位于该些像素单元外围的黑色矩阵。
在本实施例中， 所述透明导电层 20形成于所述色阻层 44上， 作为液 晶显示面板的公共电极， 与 TFT基板（未图示）上的像素电极（未图示） 形成电场以驱动液晶分子转动。 此时所述 CF基板通常为高清显示模式中 的 CF基板； 然而也不仅仅局限于此， 其还可以是需要设置透明导电电极 的其它显示模式中的 CF基板。
请参阅图 4, 为本发明 CF基板第二优选实施例的结构示意图， 在本 实施例中， 所述透明导电层 20与色阻层 44分别形成于玻璃基板 42的两 侧， 所述透明导电层 20作为静电导出层， 以将液晶显示面板中的静电导 出， 延长液晶显示面板的使用寿命。 且， 使用 ιτο层作为静电导出层时需 要在 ITO表面贴一层保护膜来保护该 ITO静电导出层， 而本发明中的使用 石墨烯透明导电层 20 制得的静电导出层则不需要贴保护层， 降低生产成 本。
当透明导电层 20作为静电导出层时， 所述 CF基板通常为平面转换 ( In-Plane Switching , IPS ) 显示模式中的 CF 基板、 或边界电场切换 ( Fringe Field Switching, FFS )显示模式中的 CF基板。 然而也不仅仅局 限于这两种显示模式中的 CF基板， 也可以是需要贴附静电导出层的其它 显示模式中的 CF基板。
请参阅图 5 , 本发明还提供一种 CF基板的制备方法， 包括以下步 骤：
步骤 11、 将生长基板置于化学气相沉积法反应器内， 通入碳源气体和 载气气体的混合气体， 在 900-1120 °C：、 40Pa-5000KPa 的条件下反应 1- 60min, 在生长基板上形成石墨烯薄膜， 所述石墨烯薄膜厚度为 0.36nm- 10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500Ω/口。
所述生长基板由镍（Ni ) 、 铜 （Cu )或钌 （Ru )制得， 优选为 Ni、
Cu或 Ru制备的金属箔， 生长基板材料不同则碳源气体和载气气体有所不 同， 本实施例中生长基板为 Cu箔， 且所述铜箔的纯度 > 99%。
所述碳源气体主要为烃类， 碳源决定化学气相沉积法的生长温度， 本 方法中碳源气体优选甲烷、 乙烯、 或乙炔， 在本实施例中碳源气体为甲 坑。
所述载气气体为氢气或氢气与氩气的混合气体， 在本实施例中所述载 气气体为氢气。
通过所述碳源气体在生长基板表面高温分解生长石墨烯， 对于 Ni等 具有较高溶碳量的金属生长基板， 碳源在裂解时产生的碳原子在高温时渗 入金属生长基板内， 在降温时再从其内部析出成核， 进而生产成石墨烯薄 膜； 对于 Cu等具有较低溶碳量的金属生长基板， 高温下气态碳源裂解生 产的碳原子吸附于金属表面， 进而成核生长成 "石墨烯岛" ， 并通过 "石 墨烯岛" 的二维长大合并得到连续的石墨烯薄膜。 CVD法制备时， 所形成 的石墨烯薄膜质量很高， 且可实现大面积生长。
步骤 12、 在石墨烯薄膜上涂布转移介质层， 得到转移介质层 /石墨烯 薄膜 /生长基板结合体。
所述转移介质层为聚甲基丙烯酸甲酯或聚二甲基丙烯酰胺。 在本实施 例中所述转移介质层为聚甲基丙烯酸甲酯。
对于仅有数纳米厚度的石墨烯薄膜而言， 其宏观强度低， 转移过程极 易破损， 所述转移介质的使用， 能够保证石墨烯薄膜在转移后结构完整、 无破损； 且对石墨烯薄膜无污染。
步骤 13、 将所述转移介质层 /石墨烯薄膜 /生长基板结合体浸渍于生长 基板腐蚀液中， 除去生长基板， 得到转移介质层 /石墨烯薄膜结合体。
生长基板腐蚀液视生长基板的不同而有所不同， 通常为 FeCl3溶液（腐 蚀 Cu生长基板等） 、 酸溶液（腐蚀 Ni生长基板等）等； 在本实施例中所述 生长基板腐蚀液为 0.1-1.5mol/L的 FeCl3溶液； 其能够腐蚀铜箔， 实现石墨 烯薄膜与生长基板的分离。
步骤 14、 提供 CF基板本体 40, 所述 CF基板本体 40包括玻璃基板 42及形成于玻璃基板 42上的色阻层 44。
具体地， 通过清洗、 涂布、 前烘烤、 曝光、 显影、 后烘烤等黄光制程 将色阻层 44形成于玻璃基板一面， 所述色阻层 44包括阵列排布的数个像 素单元及位于该些像素单元外围的黑色矩阵。
步骤 15、 将所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体 40 上， 在在室温下转印， 得到转移介质层 /石墨烯薄膜 /CF基板本体结合体。
具体地， 根据所述 CF基板本体 42的具体需求（视所制得的 CF基板 应用的显示模式而定） ， 可将所述转移介质层 /石墨烯薄膜结合体置于 CF 基板本体 40的色阻层 44上 （如图 3所示 ) , 作为液晶显示面板的公共电 极； 还可以将所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体 40 的 玻璃基板 42上（如图 4所示） ， 作为静电导出层。
步骤 16、 将所述转移介质层 /石墨烯薄膜 /CF基板本体结合体放入转移 介质层去除溶剂中清洗， 除去转移介质层， 在 CF基板本体 40上形成石墨 烯薄膜， 即在 CF基板本体 40上形成透明导电层 20。
所述转移介质层去除溶剂为能够除去转移介质层且不伤害和污染石墨 烯薄膜的溶剂， 其可根据石墨烯和转移介质层自身材料的性质进行合理选 择。 由于丙酮酒精溶液能够有效清除聚甲基丙烯酸甲酯， 且不会对石墨烯 精溶液。
具体地， 才艮据步骤 15的具体操作方式， 所述透明导电层 20形成于所 述色阻层 44 上， 则作为液晶显示面板的公共电极， 与 TFT基板（未图 示） 上的像素电极（未图示） 形成电场以驱动液晶分子转动； 此时所述 CF基板通常为高清显示模式中的 CF基板； 然而也不仅仅局限于此， 其还 可以是需要设置透明导电电极的其它显示模式中的 CF基板。
若透明导电层 20与色组层 44分别形成于玻璃基板 42的两侧， 则所 述透明导电层 20作为静电导出层， 以将液晶显示面板中的静电导出， 延 长液晶显示面板的使用寿命。 且， 使用 ΙΤΟ 层作为静电导出层时需要在 ΙΤΟ表面贴一层保护膜来保护该 ΙΤΟ静电导出层， 而本发明中的使用石墨 烯透明导电层 20 制得的静电导出层则不需要贴保护层， 降低生产成本。 当透明导电层 20作为静电导出层时， 所述 CF基板通常为平面转换（In- Plane Switching, IPS )显示模式中的 CF基板、 或边界电场切换 ( Fringe Field Switching, FFS )显示模式中的 CF基板。 然而也不仅仅局限于这两 种显示模式中的 CF基板， 也可以是需要贴附静电导出层的其它显示模式 中的 CF基板。
综上所述， 本发明的由石墨烯制成的透明导电层， 导电率可与由 ITO 制成的透明导电层相媲美， 由石墨烯制成的透明导电层的透光率可达 97%, 且本发明的由石墨烯制成的透明导电层的机械强度和柔韧性都比由 ITO 制成的透明导电层优良， 更适合应用于有机发光二极管基板等柔性基 板领域， 且使用 CVD 法制备石墨烯透明导电层时， 操作简单， 工艺条件 容易实现， 故而成本更低。 将所述石墨烯透明导电层应用于液晶显示领 域， 制得具有石墨烯透明导电层的 CF基板， 由于使用透光性能、 机械强 度和柔韧性更好的石墨烯透明导电层代替 ITO透明导电层， 因此该具有石 墨烯透明导电层的 CF基板应用于液晶显示面板中， 可以增强液晶面板的 穿透率， 减少背光的使用； 且本发明所述具有石墨烯透明导电层的 CF基 板的制备方法采用 CVD 法将石墨烯薄膜形成在生长基板上， 然后转印至 CF基板本体上， 工艺简单， 成本较低。
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

权 利 要 求
1、 一种透明导电层， 由石墨烯透明导电材料制成， 呈薄膜状， 其厚 度为 0.36nm-10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500Ω/口。
2、 一种 CF基板， 包括： CF基板本体、 及形成于 CF基板本体上的 透明导电层， 所述透明导电层由石墨烯透明导电材料制成， 呈薄膜状， 其 厚度为 0.36nm-10nm, 可见光区穿透率为 80-97% , 面电阻为 30-500 Ω / □。
3、 如权利要求 2所述的 CF基板， 其中， 所述 CF基板本体包括玻璃 基板及形成于玻璃基板上的色阻层， 该色阻层包括阵列排布的数个像素单 元及位于该些像素单元外围的黑色矩阵。
4、 如权利要求 3所述的 CF基板， 其中， 所述透明导电层位于所述色 阻层上。
5、 如权利要求 3所述的 CF基板， 其中， 所述透明导电层与色阻层分 别位于玻璃基板的两侧。
6、 一种 CF基板的制备方法， 包括如下步骤：
步骤 11、 将生长基板置于化学气相沉积法反应器内， 通入碳源气体和 载气气体的混合气体， 在 900-1120 °C：、 40Pa-5000KPa 的条件下反应 1- 60min, 在生长基板上形成石墨烯薄膜， 所述石墨烯薄膜厚度为 0.36nm- 10nm, 可见光区穿透率为 80-97%, 面电阻为 30-500Ω/口；
步骤 12、 在石墨烯薄膜上涂布转移介质层， 得到转移介质层 /石墨烯 薄膜 /生长基板结合体；
步骤 13、 将所述转移介质层 /石墨烯薄膜 /生长基板结合体浸渍于生长 基板腐蚀液中， 除去生长基板， 得到转移介质层 /石墨烯薄膜结合体；
步骤 14、 提供 CF基板本体， 所述 CF基板本体包括玻璃基板及形成 于玻璃基板上的色阻层；
步骤 15、 将所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体上， 在室温下转印， 得到转移介质层 /石墨烯薄膜 /CF基板本体结合体；
步骤 16、 将所述转移介质层 /石墨烯薄膜 /CF基板本体结合体放入转移 介质层去除溶剂中清洗， 除去转移介质层， 在 CF基板本体上形成石墨烯 薄膜， 即在 CF基板本体上形成透明导电层。
7、 如权利要求 6 所述的 CF基板的制备方法， 其中， 所述步骤 15 中， 所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体的色阻层上； 所 述步骤 16中， 透明导电层形成于所述 CF基板本体的色阻层上。
8、 如权利要求 6 所述的 CF基板的制备方法， 其中， 所述步骤 15 中， 所述转移介质层 /石墨烯薄膜结合体置于 CF基板本体的玻璃基板上； 所述步骤 16中， 透明导电层形成于所述 CF基板本体的玻璃基板上。
9、 如权利要求 6 所述的 CF基板的制备方法， 其中， 所述碳源气体为 甲烷、 乙烯、 或乙炔； 所述载气气体为氢气或氢气与氩气的混合气体； 所 述生长基板为 Ni、 Cu或 Ru制备的金属箔； 所述生长基板腐蚀液为 FeCl3溶 液或酸溶液； 所述转移介质层为聚甲基丙烯酸甲酯或聚二甲基丙烯酰胺。
10、 如权利要求 9所述的 CF基板的制备方法， 其中， 所述碳源气体为 甲烷； 所述载气气体为氢气； 所述生长基板为 Cu箔， 所述铜箔的纯度> 99%; 所述转移介质层为聚甲基丙烯酸甲酯； 所述生长基板腐蚀液为 0.1- 1.5mol/LFeCl3溶液； 所述转移介质层去除溶剂为丙酮酒精溶液。
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