CN104409177A - Large-scale preparation method for stably-doped large-area graphene transparent conductive films - Google Patents
Large-scale preparation method for stably-doped large-area graphene transparent conductive films Download PDFInfo
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Abstract
The invention relates to a preparation technology for graphene transparent conductive films, in particular to a large-scale preparation method for stably-doped large-area graphene transparent conductive films. According to the method, the doping effect and stability of the graphene transparent conductive films are improved through a sandwich structure, and a doping agent is in direct contact with the intrinsic surface of graphene and positioned between the graphene and a transparent substrate. The method comprises the following steps: firstly, forming the doping agent on the surface of the graphene or the transparent substrate on an initial substrate; secondly, combining the graphene, the doping agent and the transparent substrate; finally, separating the graphene from the initial substrate so as to prepare the stably-doped large-area graphene transparent conductive films. The graphene serves as an outer-layer protection film of the doping agent, so that the doping stability can be improved; the intrinsic surface of the graphene is in direct contact with the doping agent, so that the pollution of an interface between the graphene and the doping agent by impurities can be avoided, the doping effect of the doping agent can be improved, and the conductivity of the film can be enhanced; the transferring and doping processes of the graphene are combined, so that the large-scale preparation can be easily realized.
Description
Technical field:
The present invention relates to the technology of preparing of graphene transparent conductive film, be specially a kind of large-area graphene nesa coating large-scale preparation method of stable doping.
Background technology:
Transparent conductive film is a kind of important photoelectric material, is widely used in the photoelectric fields such as touch-screen, liquid crystal display, organic light-emitting diode display (OLED), solar cell.The development of electronics and IT products and technology and upgrading, propose the higher requirement such as flexibility, ultralight thinning, high stability to the development of nesa coating.Indium tin oxide (ITO) is the best transparent conductive film of current combination property, but ITO exists, and shortage of resources, cost are high, the problems such as pliability and poor chemical stability, cannot meet the requirement of novel transparent conducting film.
Graphene is by a kind of New Two Dimensional material with carbon element with alveolate texture of monolayer carbon atomic building.Graphene has excellent conductivity, and conductivity is 1.6 times of copper; Graphene all has excellent permeability to near-infrared, visible ray and ultraviolet light, and the light transmission of single-layer graphene reaches 97.7%; The intensity of Graphene can reach 130GPa, is more than 100 times of steel, and has excellent pliability, thermal stability and chemical stability.Therefore, Graphene can give full play to its Structure and Properties advantage as nesa coating, receives very big concern.In the grapheme material adopting distinct methods to prepare, it is high that the Graphene due to CVD growth has quality, and size is easy to the outstanding advantages amplified, and generally adopts the Graphene prepared based on CVD to prepare transparent graphene conductive film.But the Graphene of intrinsic cannot meet the requirement of high-performance nesa coating to low areal resistance, need to carry out modification to Graphene.In various method, " doping " significantly improves its conductivity by improving the carrier concentration of Graphene, is the typical method of the surface resistance reducing graphene transparent conductive film at present.Dopant mainly through with Graphene generation electron exchange or the carrier concentration being changed Graphene by dipole moment.But there is the contradiction between doping effect and stability in existing doping method: namely stable doping adulterates that effect is more weak usually and environmental stability that is that efficiently adulterate is poor.One of reason causing the problems referred to above is mainly at present to adulterate to the CVD graphene film after transfer: shift the interface of impurities left to Graphene and dopant of causing and pollute, dopant cannot form effective contact with the intrinsic surface of Graphene, limits the interactions such as electro transfer between the two.And dopant is usually located at the skin of graphene film, is directly exposed in external environment, easily produces performance degradation.In addition, separately the medium coating of transfer needed for Graphene and removal step both added cost, again reduced transfer efficiency, and first shifted the method for adulterating afterwards and make preparation process comparatively loaded down with trivial details, were therefore unfavorable for the scale doping treatment of large-area graphene.To sum up, need badly at present development can efficiently, the large-scale preparation method of the stable large-area graphene transparent conductive film that adulterates.
Summary of the invention:
The object of the present invention is to provide a kind of large-area graphene nesa coating large-scale preparation method of stable doping; doping effect and the stability of large-area graphene nesa coating is improved by sandwich; and transfer and the doping of Graphene can be realized simultaneously, be applicable to the large-area graphene nesa coating of the stable doping of scale preparation.
Technical scheme of the present invention is:
A kind of large-area graphene nesa coating large-scale preparation method of stable doping, the transfer of Graphene and doping process are united two into one, improve the doping effect of graphene transparent conductive film and stability by sandwich, dopant contacts with the intrinsic surface of Graphene and between Graphene and transparent base; First the graphenic surface in initial substrate and/or transparent base surface form dopant; Then Graphene, dopant and transparent base are combined, make dopant between Graphene and transparent base; Finally Graphene is separated with initial substrate, thus prepares the large-area graphene nesa coating of stable doping; Concrete steps are as follows:
(1) dopant is introduced on the graphenic surface in initial substrate and/or transparent base surface;
(2) Graphene in initial substrate, dopant and transparent base are combined;
(3) Graphene is separated with initial substrate.
The large-area graphene nesa coating large-scale preparation method of described stable doping, Graphene is adopt the Graphene of chemical gaseous phase depositing process growth or the Graphene of separation method growth, the average number of plies being positioned at the Graphene in initial substrate is individual layer, bilayer, few layer or multilayer, and the number of plies is less than 50 layers; The intrinsic surface of Graphene refers in particular to the graphenic surface before transfer, is not subject to the pollution of transfer medium and solution.
The large-area graphene nesa coating large-scale preparation method of described stable doping; dopant by with Graphene generation electron exchange or the carrier concentration being changed Graphene by dipole moment, typical material comprises metal, metal chloride, metal oxide, acid, one of organic molecule and polymer thereof or two or more composite materials.
The large-area graphene nesa coating large-scale preparation method of described stable doping, the method introducing dopant comprises one of immersion, printing, roll coated, blade coating, the coating of line rod, spraying, spin coating, lift, chemical vapour deposition (CVD), physical vapour deposition (PVD), evaporation coating, sputter coating or two or more.
The large-area graphene nesa coating large-scale preparation method of described stable doping, carries out reprocessing to the dopant introduced, and comprises heating 40 ~ 600 DEG C, one of cleaning and etching or two or more.
The large-area graphene nesa coating large-scale preparation method of described stable doping, is combined the Graphene in initial substrate, dopant and transparent base by adhesion or binder course; Wherein, binder course is between dopant and transparent base;
Adopt adhesion comprise electrostatic force, Van der Waals force, covalently bonded make a concerted effort, Hydrogen bonding forces, vacuum suction active force, mechanical connection power one or more;
The binder course material adopted is adhesive, comprise epoxy resin, acrylic resin, a-cyanoacrylate, organic siliconresin, furane resins, Lauxite, cellulose esters, unsaturated polyester (UP), vinyl polymer, polyethers, polyacrylate, Pioloform, polyvinyl acetal, vinyl-vinyl acetate copolymer, phenolic resins, melamine-formaldehyde resin, polyamide, polyimides, polybenzimidazoles, phenolic aldehyde-Pioloform, polyvinyl acetal, phenolic aldehyde-polyamide, phenolic aldehyde-epoxy resin, one or more of epoxy-polyamide, the thickness of adhesive tie is 10nm ~ 1mm.
The large-area graphene nesa coating large-scale preparation method of described stable doping; when initial substrate and transparent base are flexible substrate simultaneously; adopt the rolling methods of volume to volume, the comprehensive combination using adhesion or binder course to realize large-area graphene, boundary layer and transparent base.
The large-area graphene nesa coating large-scale preparation method of described stable doping, the initial substrate of employing is one of Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo metal or its alloy or two or more composite materials; Or initial substrate is one of titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, tungsten carbide or two or more composite materials; Or initial substrate is one of silicon, germanium, GaAs, gallium phosphide, cadmium sulfide, zinc sulphide, titanium oxide, manganese oxide, chromium oxide, iron oxide, cupric oxide or two or more compound; Or, the composite material that initial substrate is conductor and semiconductor.
The transparent base adopted is high molecular polymer: one or more compound of PETG, PEN, polysiloxanes, Merlon, polyethylene, polyvinyl chloride, polystyrene, polypropylene; Or transparent base is semiconductor: silica or glass; The shape of transparent base is plane, curved surface or wire side.
The large-area graphene nesa coating large-scale preparation method of described stable doping, can't harm method by matrix etching method or matrix and realizes being separated of Graphene and initial substrate; Wherein, matrix can't harm method and comprises direct stripping method or gas sparging graft process; Gas sparging graft process is see Chinese invention patent: a kind of low cost can't harm the method for transfer Graphene, patent No. ZL 201110154465.9.
The large-area graphene nesa coating large-scale preparation method of described stable doping, the Diagonal Dimension of the transparent graphene conductive film after doping reaches more than 20 inches.
Design philosophy of the present invention is:
The present invention improves doping effect and the stability of graphene transparent conductive film by sandwich: adulterate to the Graphene in initial substrate before transfer, dopant directly contacts with the intrinsic surface of Graphene; After transfer, dopant is between Graphene and transparent base.Because the intrinsic surface of Graphene directly contacts with dopant, avoid the pollution of impurity to interface between the two, the doping effect of dopant can be promoted, thus improve the conductivity of film; Meanwhile, Graphene, as the outer protective film of dopant, improves the stability of doping.In addition, the transfer of Graphene and doping process unite two into one by the method, and technique is simple and the mode of volume to volume can be adopted to realize, and are easy to realize scale preparation and automated production.
Feature of the present invention and beneficial effect are:
1. the present invention adopts the method for " first adulterate and shift afterwards ", by the mode that the intrinsic surface of Graphene in initial substrate directly contacts with dopant, avoid conventional " first shift and adulterate afterwards " method to the pollution at interface between Graphene and dopant, electro transfer between the two and interaction can be promoted, thus improve the doping effect to Graphene.
2. the present invention adopts Graphene as outer membrane, for the protection of dopant, prevents dopant to be directly exposed in environment and produces performance degradation.
3. " doping " and " transfer " process separate in conventional method unites two into one by the present invention; the simple controllability of technique is high; be expected to the scale preparation realizing large area (Diagonal Dimension is generally 1 ~ 20 inch, even can reach more than 20 inches) doped graphene transparent conductive film.
4. each processing step of the present invention is all compatible with typical volume to volume rolling process, easily realizes the continuous seepage of automation.
Accompanying drawing illustrates:
Fig. 1 (a)-(b) is the schematic flow sheet of the large-area graphene nesa coating of the stable doping of scale preparation.Wherein, Fig. 1 (a) is flow process one; Fig. 1 (b) is flow process two.
Embodiment:
Below by drawings and Examples, the present invention is described in further detail.
As shown in Fig. 1 (a)-(b), different from the combination of transparent base according to Graphene, dopant, the process that the present invention prepares the large-area graphene nesa coating of stable doping is divided into the following two kinds:
A () uses that binder course realizes Graphene in initial substrate, dopant is combined with transparent base, form " initial substrate/Graphene/dopant/binder course/transparent base " composite material, then initial substrate and Graphene are peeled off, thus obtain the transparent conductive film that structure is " Graphene/dopant/binder course/transparent base "; Wherein, can graphenic surface (route is 1.) in initial substrate, or transparent base surface (route is 2.) introduces dopant.
B () uses that adhesion realizes Graphene in initial substrate, dopant is combined with transparent base, form " initial substrate/Graphene/dopant/transparent base " composite material, then initial substrate and Graphene are peeled off, thus obtain " Graphene/dopant/transparent base " transparent conductive film; Wherein, can graphenic surface (route is 1.) in initial substrate, or transparent base surface (route is 2.) introduces dopant.
Embodiment 1
Adopt metal copper foil as initial substrate, adopt molybdenum oxide as dopant, adopt pet film as target substrate, adopt the mode of hot binding.Utilize CVD (in the present embodiment, metal copper foil can change copper sheet or the copper coin of different size into, monocrystalline or polycrystalline, and thickness is greater than 10 μm, and the present embodiment is 25 μm) growing graphene on metal copper foil.After growing the Copper Foil cooling having Graphene, utilize the method for evaporation coating to form Electrochromic Molybdenum Oxide Coatings at Graphene/copper foil surface, thickness is 3nm.By this film in argon gas atmosphere, 300 DEG C process 1 hour.By the method for volume to volume hot-rolling pressure (or hot plate pressure), the Graphene that Copper Foil grows, molybdenum oxide and pet film are directly pressed together, pressure is less than 2MPa (the present embodiment is 1MPa), hot pressing temperature is 120 ~ 140 DEG C, forms " PETG/molybdenum oxide/Graphene/Copper Foil " composite material.This composite material is connected the negative pole of upper constant-current supply, with another sheet platinized platinum as positive pole, in the present embodiment, electrolyte is the NaOH aqueous solution of 1mol/L, " PETG/molybdenum oxide/Graphene/Copper Foil " immersed after in solution, apply 1 Ampere currents, electrolytic process applied voltage is 8 ~ 16 volts, the operating temperature of electrolytic process is at 20 ~ 50 DEG C, and the gas that electrolysis produces is hydrogen (H2).After " PETG/molybdenum oxide/Graphene " is separated completely with Copper Foil, " PETG/molybdenum oxide/Graphene " is taken out from NaOH solution, rinse and bone dry with water, the graphene film of the molybdenum oxide doping on PETG matrix can be obtained.
In the present embodiment, the performance of the large-area graphene nesa coating of stable doping is as follows: Diagonal Dimension is 20 inches, centre plane resistance is 680 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 2
Difference from Example 1 is:
Adopt electrostatic force as adhesion.(voltage producing electrostatic is not less than 0.1kV to produce electrostatic force on " molybdenum oxide/Graphene/Copper Foil " (or on pet film surface) to utilize electrostatic generator, the present embodiment is 15kV), adopt the method for roll-in or plate pressure that " molybdenum oxide/Graphene/Copper Foil " and pet film are pressed together by electrostatic force that (pressure is less than 1MPa, the present embodiment is 0.1MPa), form " PETG/molybdenum oxide/Graphene/Copper Foil " composite material.
In the present embodiment, electrolyte is the NaOH aqueous solution of 8mol/L, and the operating temperature of electrolytic process is at 35 ~ 40 DEG C, and electrolytic process applied voltage is at 45 ~ 50 volts, and electric current is at 7 amperes, and the gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of the graphene transparent conductive film of stable doping is as follows: Diagonal Dimension is 4 inches, and centre plane resistance is 1070 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 3
Difference from Example 1 is:
Adopt different initial substrate material.In the present embodiment, metal copper foil can change into the metals such as nickel, cobalt, molybdenum and alloy (corronil, Mo-Ni alloy, golden nickel alloy etc.) thereof paillon foil or on silicon chip the metallic film of stable bond, and the metal carbides such as titanium carbide, molybdenum carbide, tungsten carbide, or other semiconductor such as Si) as initial substrate, utilize distinct methods at its superficial growth single or multiple lift Graphene.
In the present embodiment, electrolyte is the NaOH aqueous solution of 3mol/L, and the operating temperature of electrolytic process is at 20 ~ 30 DEG C, and electrolytic process applied voltage is at 10 ~ 12 volts, and electric current is at 4 amperes; The gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of the graphene transparent conductive film of doping is as follows: Diagonal Dimension is 4 inches, and centre plane resistance is 320 ohms/square, and light transmittance (550 nanometer) is 89%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 4
Difference from Example 1 is:
Adopt different dopants.In the present embodiment, molybdenum oxide can change two trifluoromethanesulfonimide (TFSA), 7 into, 7,8, the organic substances such as 8-four cyano benzoquinone bismethane (TCNQ), benzimidazole, fluororesin (CYTOP), Kynoar (PVDF), Polyglycolic acid fibre/polystyrolsulfon acid (PEDOT:PSS) or and solution, adopt coating or deposition method be formed in copper foil surface or pet film surface.In the present embodiment, realize being separated of Graphene and Copper Foil by matrix etching method." PETG/dopant/Graphene/Copper Foil " is placed in the aqueous solution (molar concentration 1M) of iron chloride, after Copper Foil dissolves completely, " PETG/dopant/Graphene " is taken out from etching solution, rinses and bone dry with water.
In the present embodiment, the performance of the graphene transparent conductive film of TFSA doping is as follows: Diagonal Dimension is 4 inches, and centre plane resistance is 620 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 5
Difference from Example 1 is:
Adopt different initial substrate and dopant.In the present embodiment, metal copper foil can change the oxidation resistant metals such as platinum, ruthenium, iridium into.Molybdenum oxide can change the oxidizing acids such as red fuming nitric acid (RFNA) into, or the aqueous solution of the metal chloride such as chlorauride.Roll coated, spraying, spin coating or czochralski method is adopted to be formed in Graphene/initial substrate surface.
In the present embodiment, electrolyte is the NaOH aqueous solution of 0.5mol/L, and the operating temperature of electrolytic process is at 5 ~ 10 DEG C, and electrolytic process applied voltage is at 1 ~ 3 volt, and electric current is at 2 amperes; The gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of the graphene transparent conductive film of chlorauride doping is as follows: Diagonal Dimension is 2 inches, and centre plane resistance is 410 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 6
Difference from Example 1 is:
Adopt different transparent bases.In the present embodiment, PETG can change other thin polymer films such as PEN film, polysiloxane film, polycarbonate film, polyethylene film, polyvinyl chloride film, polystyrene film or polypropylene film into, or changes silica or glass etc. into.
In the present embodiment, electrolyte is the NaOH aqueous solution of 1mol/L, and the operating temperature of electrolytic process is at 30 ~ 40 DEG C, and electrolytic process applied voltage is at 20 ~ 25 volts, and electric current is at 5 amperes; The gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of the graphene transparent conductive film being matrix with PEN film is as follows: Diagonal Dimension is 4 inches, centre plane resistance is 680 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 7
Difference from Example 1 is:
Adopt adhesive as binder course.In the present embodiment, adopt PUR as bonding layer material, adopt the method for hot pressing (roll-in or plate pressure) that " molybdenum oxide/Graphene/Copper Foil " and pet film are pressed together by PUR that (pressure is less than 1MPa, and the present embodiment is 0.1MPa; Temperature: 80 DEG C ~ 150 DEG C, the present embodiment is 120 DEG C).
In the present embodiment, electrolyte is the NaOH aqueous solution of 4mol/L, and the operating temperature of electrolytic process is at 50 ~ 60 DEG C, and electrolytic process applied voltage is at 5 ~ 10 volts, and electric current is at 3 amperes; The gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of graphene transparent conductive film is as follows: Diagonal Dimension is 14 inches, and centre plane resistance is 1000 ohms/square, and light transmittance (550 nanometer) is 95%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 8
Difference from Example 7 is:
Adopt different adhesive as binder course.PUR can change cellulose esters into, vinyl polymer, polyester, polyethers, polyamide, polyacrylate, a-cyanoacrylate, Pioloform, polyvinyl acetal, vinyl-vinyl acetate copolymer, epoxy resin, phenolic resins, Lauxite, melamine-formaldehyde resin, organic siliconresin, furane resins, unsaturated polyester (UP), acrylic resin, polyimides, polybenzimidazoles, phenolic aldehyde-Pioloform, polyvinyl acetal, phenolic aldehyde-polyamide, phenolic aldehyde-epoxy resin, epoxy-polyamide etc., corresponding curing mode can adopt pressurization respectively, heating, illumination, add curing agent etc.
In the present embodiment, electrolyte is the NaOH aqueous solution of 2mol/L, and the operating temperature of electrolytic process is at 10 ~ 20 DEG C, and electrolytic process applied voltage is at 30 ~ 40 volts, and electric current is at 4 amperes; The gas that electrolysis produces is hydrogen.
In the present embodiment, as follows as the performance of the graphene transparent conductive film as binder course using epoxide-resin glue: Diagonal Dimension is 4 inches, centre plane resistance is 480 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment 9
Difference from Example 1 is:
In order to improve the separating rate of Graphene and Copper Foil, in original electrolyte, add the ammonium persulfate of weak erosive.In the present embodiment, containing NaOH and the 0.01mol/L ammonium persulfate of 0.8mol/L in electrolyte, the operating temperature of electrolytic process at 8 ~ 10 DEG C, applied voltage at 2 ~ 3 volts, 3 amperes, electric current; The gas that electrolysis produces is hydrogen.
In the present embodiment, the performance of the large-area graphene nesa coating of stable doping is as follows: Diagonal Dimension is 4 inches, centre plane resistance is 690 ohms/square, and light transmittance (550 nanometer) is 96%, and the resistance variations of adulterating in latter 30 days is less than 10%.
Embodiment result shows, the inventive method improves the doping effect of graphene transparent conductive film and stability by sandwich, and dopant directly contacts with the intrinsic surface of Graphene and between Graphene and transparent base.First the graphenic surface in initial substrate or transparent base surface form dopant, then Graphene, dopant and transparent base are combined, finally Graphene is separated with initial substrate, thus prepares the large-area graphene nesa coating of stable doping.Graphene, as the outer protective film of dopant, improves the stability of doping; The intrinsic surface of Graphene directly contacts with dopant, avoids impurity to the pollution at interface between the two, improves the doping effect of dopant, thus improve the conductivity of film.The transfer of Graphene and doping process are united two into one, technique is simple and adopt the mode of volume to volume to realize, and is easy to realize scale preparation.The method can be used as the Perfected process of the large-area graphene nesa coating of the stable doping of a kind of scale preparation, for the application of High-performance graphene nesa coating in the high-end photoelectric devices such as liquid crystal display, organic light-emitting diode display (OLED), solar cell is laid a good foundation.
Claims (10)
1. the large-area graphene nesa coating large-scale preparation method of a stable doping, it is characterized in that: the transfer of Graphene and doping process are united two into one, improve the doping effect of graphene transparent conductive film and stability by sandwich, dopant contacts with the intrinsic surface of Graphene and between Graphene and transparent base; First the graphenic surface in initial substrate and/or transparent base surface form dopant; Then Graphene, dopant and transparent base are combined, make dopant between Graphene and transparent base; Finally Graphene is separated with initial substrate, thus prepares the large-area graphene nesa coating of stable doping; Concrete steps are as follows:
(1) dopant is introduced on the graphenic surface in initial substrate and/or transparent base surface;
(2) Graphene in initial substrate, dopant and transparent base are combined;
(3) Graphene is separated with initial substrate.
2. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: Graphene is adopt the Graphene of chemical gaseous phase depositing process growth or the Graphene of separation method growth, the average number of plies being positioned at the Graphene in initial substrate is individual layer, bilayer, few layer or multilayer, and the number of plies is less than 50 layers; The intrinsic surface of Graphene refers in particular to the graphenic surface before transfer, is not subject to the pollution of transfer medium and solution.
3. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1; it is characterized in that: dopant by with Graphene generation electron exchange or the carrier concentration being changed Graphene by dipole moment, typical material comprises metal, metal chloride, metal oxide, acid, one of organic molecule and polymer thereof or two or more composite materials.
4. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: the method introducing dopant comprises one of immersion, printing, roll coated, blade coating, the coating of line rod, spraying, spin coating, lift, chemical vapour deposition (CVD), physical vapour deposition (PVD), evaporation coating, sputter coating or two or more.
5. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: reprocessing is carried out to the dopant introduced, comprise heating 40 ~ 600 DEG C, one of cleaning and etching or two or more.
6. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: by adhesion or binder course, the Graphene in initial substrate, dopant and transparent base are combined; Wherein, binder course is between dopant and transparent base;
Adopt adhesion comprise electrostatic force, Van der Waals force, covalently bonded make a concerted effort, Hydrogen bonding forces, vacuum suction active force, mechanical connection power one or more;
The binder course material adopted is adhesive, comprise epoxy resin, acrylic resin, a-cyanoacrylate, organic siliconresin, furane resins, Lauxite, cellulose esters, unsaturated polyester (UP), vinyl polymer, polyethers, polyacrylate, Pioloform, polyvinyl acetal, vinyl-vinyl acetate copolymer, phenolic resins, melamine-formaldehyde resin, polyamide, polyimides, polybenzimidazoles, phenolic aldehyde-Pioloform, polyvinyl acetal, phenolic aldehyde-polyamide, phenolic aldehyde-epoxy resin, one or more of epoxy-polyamide, the thickness of adhesive tie is 10nm ~ 1mm.
7. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 6; it is characterized in that: when initial substrate and transparent base are simultaneously for flexible substrate; adopt the rolling methods of volume to volume, the comprehensive combination using adhesion or binder course to realize large-area graphene, boundary layer and transparent base.
8. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: the initial substrate of employing is one of Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo metal or its alloy or two or more composite materials; Or initial substrate is one of titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, tungsten carbide or two or more composite materials; Or initial substrate is one of silicon, germanium, GaAs, gallium phosphide, cadmium sulfide, zinc sulphide, titanium oxide, manganese oxide, chromium oxide, iron oxide, cupric oxide or two or more compound; Or, the composite material that initial substrate is conductor and semiconductor;
The transparent base adopted is high molecular polymer: one or more compound of PETG, PEN, polysiloxanes, Merlon, polyethylene, polyvinyl chloride, polystyrene, polypropylene; Or transparent base is semiconductor: silica or glass; The shape of transparent base is plane, curved surface or wire side.
9. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: can't harm method by matrix etching method or matrix and realize being separated of Graphene and initial substrate; Wherein, matrix can't harm method and comprises direct stripping method or gas sparging graft process; Gas sparging graft process is see Chinese invention patent: a kind of low cost can't harm the method for transfer Graphene, patent No. ZL 201110154465.9.
10. according to the large-area graphene nesa coating large-scale preparation method of stable doping according to claim 1, it is characterized in that: the Diagonal Dimension of the transparent graphene conductive film after doping reaches more than 20 inches.
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| CN110133918A (en) * | 2019-05-24 | 2019-08-16 | 宁波石墨烯创新中心有限公司 | Graphene transparent conductive film, preparation method and liquid crystal film |
| CN110643076A (en) * | 2019-08-14 | 2020-01-03 | 浙江海洋大学 | Preparation method of transparent substrate film of flexible electronic device |
| CN112489878A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院金属研究所 | Method for synchronously improving conductivity and light transmittance of two-dimensional material |
| CN112489878B (en) * | 2019-09-11 | 2022-05-31 | 中国科学院金属研究所 | Method for synchronously improving electrical conductivity and light transmittance of two-dimensional material |
| CN112736176A (en) * | 2019-10-14 | 2021-04-30 | 中国科学院金属研究所 | Method for improving luminous efficiency of light-emitting diode |
| CN110963484A (en) * | 2019-12-23 | 2020-04-07 | 中国科学院长春光学精密机械与物理研究所 | Doping layer-assisted large-area high-quality graphene nondestructive transfer method |
| CN111333058A (en) * | 2020-03-03 | 2020-06-26 | 中国科学院长春光学精密机械与物理研究所 | Double-sided doping method of single-layer graphene and double-sided doping method of multi-layer graphene |
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