CN102569432B - Transparent electrode material and preparation method thereof - Google Patents
Transparent electrode material and preparation method thereof Download PDFInfo
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- CN102569432B CN102569432B CN201010593306.4A CN201010593306A CN102569432B CN 102569432 B CN102569432 B CN 102569432B CN 201010593306 A CN201010593306 A CN 201010593306A CN 102569432 B CN102569432 B CN 102569432B
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a transparent electrode material and a preparation method thereof. The material comprises a substrate and a conductive layer attached on the substrate, wherein the conducive layer contains graphene and metal, the square resistance of the conductive layer is 0.001-1000 omega/sq, the transmittance of the conducive layer in a visible light region is 70-98%, and the transmittance in an infrared light region is 70-98%. As a transparent electrode has a compound structure containing the metal and the graphene, the transparent electrode has excellent performances of high transmittance and low resistance and can enhance the structural stability and the resistance to bending of the transparent electrode due to the addition of the graphene, further an electron transport channel is added and finally the electrical conductivity of the transparent electrode is improved. The transparent electrode material disclosed by the invention has extensive uses in the aspects of optoelectronic devices, photoelectric detectors and semiconductor light emitting, particularly the aspects of flexible solar cells, flexible display devices and other flexible devices. The preparation method disclosed by the invention is simple in process and easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of transparent electrode material and preparation method thereof.
Background technology
At present, the photoelectric device such as solar cell, semiconductor detector, electroluminescence and flat-panel monitor all need low resistance, high light transmittance can transparency electrode.And flexible photoelectric device of new generation more needs resistant to bending transparency conductive electrode on this basis.Transparent conductive oxide film (TCOs), metal film, carbon nano-tube and Graphene are usually used as the transparency electrode of above-mentioned device.In TCOs, be widely used as the ITO (tin-doped indium oxide) of indium oxide system.But there are many deficiencies in ITO, for example: the metals such as relative Ag, Ni, the resistivity of ITO is higher can not meet the more demand for development of low-resistivity of above-mentioned device, and the scarcity of indium reserves makes involving great expense of ITO, ITO is unstable in flexible substrates, not resistance to bending, so wish to develop its substitution material.Carbon nano-tube light transmittance is only better than ITO in infrared region.Under state-of-the-art, graphene conductive is not as metals such as Ag, Ni, but Graphene has good flexibility.Metal film conductivity and light transmission are better, but unstable on flexible substrate.
Summary of the invention
The object of the invention is in order to overcome existing transparent electrode material transmitance low, resistivity is higher, lack the flexible and shortcoming of resistance to deflection not, provide a kind of transmitance high, conduct electricity very well, transparent electrode material that the metal film of pliability excellence and Graphene are compound and preparation method thereof.
The invention provides a kind of transparent electrode material, described transparent electrode material comprises substrate and is attached to this on-chip conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, the light transmittance in visible region of described conductive layer is 70-98%, is 70-98% at the light transmittance of infrared light region.
The present invention also provides the preparation method of above-mentioned transparent electrode material, the method comprises, on substrate, form conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region.
Transparency electrode of the present invention is because the composite construction that contains metal and Graphene, make it not only there is high light transmittance, low-resistance excellent properties, and because of structural stability and the resistance to bend(ing) of having strengthened transparency electrode of adding of Graphene, thereby further increase electron propagation ducts, finally improve the conductivity of transparency electrode and (inferred that this is because the flexibility of graphene film can be improved metal film in on-chip performance; The conductivity of Graphene can play electron bridge beam action after compound with metal film, further increases the conductivity of metal film; And Graphene is all very high in ultraviolet, visible ray, infrared light district transmitance, can not affect the light transmission of metal film.
Transparent electrode material of the present invention is at photoelectric device, photodetector and semiconductor light emitting, especially of many uses aspect the flexible device such as flexible solar battery, flexible display.Preparation method's of the present invention technique is simple, is easy to realize suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the schematic diagram of a type transparent electrode material.
Fig. 2 is the schematic diagram of b type transparent electrode material.
Fig. 3 is the schematic diagram of another kind of b type transparent electrode material.
Fig. 4-7th, the front view of a type of the present invention or b type transparent electrode material and a left side (right side) view.
Description of reference numerals
1 is substrate; 2 is metal level; 3 is graphene layer; 4 is the conductive layer being formed by the mixture of Graphene and metal.
Embodiment
The invention provides a kind of transparent electrode material, this material comprises substrate and is attached to this on-chip conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, the light transmittance in visible region of described conductive layer is 70-98%, is 70-98% at the light transmittance of infrared light region; Under preferable case, the square resistance of described conductive layer is 0.001-100 Ω/sq, and the light transmittance in visible region of described conductive layer is 80-98%, is 80-98% at the light transmittance of infrared light region.
And transparent electrode material of the present invention bending 1000 times and each all bending rear resistance in 90 ° on flexible substrate decline and are less than 2%.
In transparent electrode material of the present invention, described conductive layer can be formed by the mixture layer of Graphene and metal, now, the weight ratio of described Graphene and metal can be 1: 0.01-10000, the number of plies of the mixture layer of described Graphene and metal can be 1-20 layer, and the thickness of the mixture layer of Graphene and metal can be 0.2-300nm described in every one deck; In order to obtain better light transmission and flexible, under preferable case, the weight ratio of described Graphene and metal is preferably 1: 0.1-1000, the thickness of the mixture layer of Graphene and metal is preferably 0.2-100nm described in every one deck.
Under preferable case, described conductive layer in transparent electrode material of the present invention also can be formed by graphene layer and replacing property of metal level, the thickness of described graphene layer can be 0.2-10nm, the number of plies of described graphene layer can be 1-10 layer, the thickness of described metal level can be 0.2-300nm, and the number of plies of described metal level can be 1-10 layer.In order to obtain better light transmittance and flexible, under preferable case, the thickness of described graphene layer is 0.2-3nm, and the number of plies of described graphene layer can be 1-2 layer; The thickness of described metal level is 0.5-10nm, and the number of plies of described metal level can be 1-2 layer.It should be explicitly made clear at this point, above-mentioned thickness refers to respectively the average thickness of graphene layer and metal level.
Under preferable case, the metal film that described metal level in the present invention is patterning, described metal film be preferably select the continuous metal film of free micro-nano becket composition, the discontinuous metal film being formed by micro-nano becket, by regular hole arrange the two-dimensional metallic microgrid that forms, by irregular hole arrange the two-dimensional metallic microgrid forming, the metal film being formed by continuous metal island, the metal film being formed by discontinuous metal island and the metal film that formed by one-dimensional metal nm line in one.In order to obtain better conductivity, light transmission and flexible, more preferably arranges by regular hole the two-dimensional metallic microgrid forming.
In transparent electrode material of the present invention, described metal can, for being selected from one or more in silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, be preferably gold or silver.
In the present invention, related Graphene can be the conventional various Graphenes that use in this area, the present invention to the number of plies of described Graphene without particular/special requirement, it can be the mixture of single-layer graphene and multi-layer graphene, the Graphene of described multilayer is generally the multi-layer graphene of 2-10 layer, in addition, described Graphene is the Graphene that is all made up of carbon atom or doped with heteroatomic Graphene.Wherein, describedly can be selected from one or more in nitrogen, oxygen, sulphur, boron and phosphorus doped with the hetero-atom in heteroatomic Graphene.
In the present invention, can select different substrates according to different demands, in transparent electrode material of the present invention, described substrate can be is 90-100% at the light transmittance of visible region, be preferably 92-98%, be 90-100% at the light transmittance of infrared light region, be preferably one or more in transparent polymeric film, glass and the quartz of 92-98%, described transparent polymeric film can be one or more in polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and polyacrylate film.
Conductive layer on transparent electrode material provided by the invention has three types, a kind of is the mixture layer that Graphene and metal form, another kind of is first formation graphene layer alternately, form again metal level, also having a kind of is first formation metal level alternately, form again graphene layer, according to preparation method can by rear both be divided into a class.
Therefore, the present invention is directed to dissimilar conductive layer, two kinds of corresponding preparation methods are provided.
The invention provides the preparation method of the transparent electrode material that above-mentioned conductive layer forms by the mixture of metal and Graphene, the method comprises, form conductive layer at substrate, described conductive layer is formed by the mixture layer of Graphene and metal, the square resistance of the described conductive layer forming is 0.001-1000 Ω/sq, described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region.
The present invention to the described method that forms conductive layer on substrate without particular/special requirement, for example can carry out as follows: the dispersion liquid that contains Graphene and metal is attached to substrate surface, at 60-200 DEG C, place after 1-120 minute, more preferably at 80-120 DEG C, place 20-40min, then place 2-10min at 140-160 DEG C, then repeat following steps 0-19 time: the surface that the dispersion liquid that contains Graphene and metal is attached to the mixture layer of obtained Graphene and metal, at 60-200 DEG C, place after 1-120 minute, obtain the transparent electrode material with conductive layer, more preferably at 80-120 DEG C, place 20-40min, then place 2-10min at 140-160 DEG C.Wherein, repeat step and can determine whether as required to carry out, and the number of times carrying out, by above-mentioned steps, can in transparent substrates, form the conductive layer of 1-20 layer.
In above-mentioned preparation method, described in contain Graphene and metal dispersion liquid in the concentration of Graphene can be for 0.001-10mg/mL, the concentration of metal can be 0.01-100mg/mL; For handled easily, described in contain Graphene and metal dispersion liquid in the concentration of Graphene be preferably 0.01-1mg/mL, the concentration of metal is preferably 0.1-10mg/mL.
Under preferable case, the consumption that contains each time the dispersion liquid of Graphene and metal is that the thickness of the mixture layer that contains Graphene and metal described in every one deck in the transparent electrode material that makes to obtain is 0.2-300nm.
In the present invention, the transparent electrode material of preparing by the method is called to a type transparent electrode material.As shown in Figure 1, wherein, 1 is substrate; 4 is the conductive layer being formed by the mixture of Graphene and metal, Fig. 1 only illustrates the two-layer transparent electrode material in one embodiment of the present invention, one skilled in the art may determine that the conductive layer more being formed by the mixture of Graphene and metal can form successively on the conductive layer being formed by the mixture of Graphene and metal.
In above-mentioned preparation method, the dispersion liquid that contains Graphene and metal is attached to transparent substrates surface or is attached to the surperficial method of mixture layer of obtained Graphene and metal that there is no particular limitation, for example can, for being selected from one or more in spin-coating method, spraying process, knife coating and infusion process, be preferably spin-coating method.
The method according to this invention, the dispersion liquid of described Graphene and metal can provide with various forms, for example solation, described in contain Graphene and metal dispersion liquid can be prepared with reference to prior art, the present invention, without particular/special requirement, does not repeat them here.
The present invention also provides the preparation method of the transparent electrode material that above-mentioned conductive layer alternately forms by graphene layer and metal level, the method comprises, on substrate, alternately form metal level and graphene layer, to form conductive layer on substrate, the square resistance of described conductive layer is 0.001-1000 Ω/sq, described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region.
In the present invention, the transparent electrode material that conductive layer is alternately formed by graphene layer and metal level is called b type transparent electrode material, comprising first form the transparent electrode material that forms metal level after graphene layer on substrate, as shown in Figure 2, wherein, 1 is substrate; 2 is metal level; 3 is graphene layer; With on substrate, first form the transparent electrode material that forms graphene layer after metal level, as shown in Figure 3, wherein, 1 is substrate; 2 is metal level; 3 is graphene layer.Fig. 2 and Fig. 3 just illustrate respectively the two-layer transparent electrode material in two kinds of execution modes of the present invention, one skilled in the art may determine that more graphene layer or metal level can form successively on metal level and graphene layer.
The method according to this invention, under preferable case, the thickness of described metal level can be 0.2-300nm, is preferably 0.5-10nm, the number of plies of described metal level can be 1-10 layer, is preferably 1-2 layer; The thickness of described graphene layer can be 0.2-10nm, is preferably 0.2-3nm; The number of plies of described graphene layer can be 1-10 layer, is preferably 1-2 layer.
In above-mentioned preparation method, to the method for described formation graphene layer, there is no particular limitation, can carry out with reference to prior art, for example, can, for being selected from spin-coating method, spraying process, knife coating, infusion process or czochralski method, be preferably spin-coating method; To the method for described formation metal level, also there is no particular limitation, for example can, for being selected from template, electrospinning weave, stamped method, self-assembly method, etching method, sedimentation, electromagnetic field guidance method, sputtering method, sol-gal process, spin-coating method, spraying process, electrostatic spinning or knife coating, be preferably template.
Due to the metal using in preparation method of the present invention, substrate and form the described Graphene of conductive layer and thickness and the kind etc. of the mixture layer of metal, graphene layer all with product in related identical, do not repeat them here.
Below in conjunction with embodiment, the present invention is further described.
In following examples, by ultraviolet/visible/near infrared spectrophotometer (PerkinElmer Lambda950) mensuration visible light transmissivity and infrared light transmitance; With two electrical measurement four point probe testers (Guangzhou four point probe science and technology RTS-9) mensuration square resistance; Scanning probe microscopy test (DigitalInstruments Dimension 3100) for film thickness; With the surface topography of SEM ESEM (HIT, HitachiS-4800) test material, size (as average grain diameter etc.).
Preparation example 1
The preparation of graphene oxide colloidal sol
To the concentration of 1500g be the natural flaky graphite that adds 5.0g in the concentrated sulfuric acid of 98 % by weight (particle diameter be 200 μ m), the sodium nitrate of 5.0g and the potassium permanganate of 25.0g, by gained mixture, under the condition of ice bath of 0 DEG C, (making the temperature of mixture by ice bath is 0 DEG C) stirs after 5h, then at 30 DEG C, stirs 10h again; Then in gained mixture, add 500mL water to dilute, then be warming up to 70 DEG C and stir after 2h, the concentration that adds 6mL is the hydrogen peroxide of 30 % by weight, after stirring 1h, filter, then be the hydrochloric acid centrifuge washing of 10 % by weight by concentration by the filter cake obtaining, then use again deionized water centrifuge washing, gluey product after washing is joined in the deionized water of 40mL, under the power of 200W, ultrasonic dispersion obtains graphene oxide colloidal sol (content of graphene oxide is 20 % by weight, and the content of water is 80 % by weight).
Embodiment 1
The present embodiment is the preparation method for b type transparent electrode material of the present invention is described.
(1) prepare porous anodic alumina template: adopt two step anode oxidation methods (according to HidekiMasuda and Kenji Fukuda, Ordered Metal Nanohole Arrays Made by a Two-StepReplication of Honeycomb structures of Anodic Alumina, SCIENCE, 268 (9) 1995) method providing in) prepare porous anodic aluminium oxide sheet, the aperture of measuring this porous anodic aluminium oxide sheet by ESEM is 50nm, and pitch of holes is 150nm;
(2) electron beam evaporation plating metal level: evaporation layer of metal silver on the anodic alumina film that deposited by electron beam evaporation instrument (Edwars, AUTO 500) obtains to step (1), thickness 3nm;
(3) remove alumina formwork: have the anodic alumina film below of argent to place quartz plate (the magnificent quartzy electrical apparatus factory in Jinzhou at step (2) evaporation, size is 2cm × 2cm, thickness is 1mm), in the phosphoric acid solution that is 1% in concentration, dissolve anodised aluminium, perforated metal silver grid natural subsidence is to quartz plate; With unnecessary phosphoric acid and metal ion on deionized water washing quartz plate, dry 4h at 100 DEG C;
(4) prepare graphene oxide film: on the quartz plate that has metal grill obtaining in step (3) with spin coating instrument the graphene oxide colloidal sol to obtain in the thick preparation example 1 of rotating speed spin coating one deck 6nm of 4000rpm, at 100 DEG C dry 10 minutes;
(5) thermal reduction graphene oxide: under the protection of Ar gas; the thickness that contains that step (4) is obtained is that the quartz plate of the graphene oxide film of 0.8nm is put into quartz ampoule; then quartz ampoule is put into tube furnace; slowly be warmed up to 800 DEG C of heating 10 minutes with 200 DEG C per hour of heating rate; then under the protection of Ar gas, slowly cool to room temperature in stove, reduction obtains the transparent electrode material that contains Graphene and argent.The front view of transparent electrode material and a left side (right side) view is as shown in A and B in Fig. 4.
The metal layer thickness of transparent electrode material is 3nm, and the metal level number of plies is 1 layer; Graphene layer thickness is 0.8nm, and the graphene layer number of plies is 1 layer.
Transparent electrode material is 92% at visible region light transmittance, infrared light district light transmittance is 92%, square resistance 5 Ω/sq.
Embodiment 2
The present embodiment is the preparation method for b type transparent electrode material of the present invention is described.
(1) method of chemical vapour deposition (CVD) is prepared nitrogen-doped graphene: with coating machine (KYUY Branch Tech technical development Co., Ltd, model SBC-2), taking Ni as target material, sedimentation time 20s, in quartz plate (the magnificent quartzy electrical apparatus factory in Jinzhou, size is 2cm × 2cm, and thickness is 1mm) the upper thick Ni of hot evaporation 50nm.Quartz plate is put into quartz ampoule, logical hydrogen (20sccm) and argon gas (100sccm), in the time that body of heater central temperature is elevated to 800 DEG C, pass into the CH4 of 60sccm and the NH3 of 60sccm, quartz ampoule is put into body of heater center, after 10 minutes, by sample cool to room temperature under hydrogen stream, obtain the graphene film of nitrogen doping, the Ni on the phosphoric acid solution dissolving films that is 1% by concentration, uses deionized water graphite water alkene surface three times.
(2) prepare polystyrene microsphere: in 500mL there-necked flask, add 10mL styrene and 150mL water, logical nitrogen purge gas 15min, stirs 20min at 70 DEG C of waters bath with thermostatic control, adds 0.2g potassium peroxydisulfate, react 24h at 70 DEG C.Centrifugation obtain polystyrene microsphere list aqueous dispersion (phenylethylene micro ball concentration is 10 % by weight, the average grain diameter of phenylethylene micro ball be 1.3 μ m).
(3) prepare pattern metal film taking polystyrene microsphere monofilm as template: in 4.95mL polystyrene microsphere list aqueous dispersion (phenylethylene micro ball concentration is 10 % by weight), add 0.05mL styrene and 5mL absolute ethyl alcohol, again to the sulfuric acid (concentration is 98%) that adds 0.15 μ L in this solution, ultrasonic 15 minutes, put at container bottom the surface that above-mentioned steps (1) processes and have the quartz plate of graphene film, release the liquid in container, with deionized water washing three times.By plasma etching (RIE) system (SENTECH, ETCHCAB200), use oxygen rie 10s, polystyrene microsphere particle diameter is reduced to 1 μ m.With magnetic control sputtering device (ULVAC Inc, ACS-400-C4), at operating pressure 0.5Pa, under power 40W condition, sputter 10s vertical with quartz plate, plated metal Al in polystyrene microsphere space, obtain the Al that 3nm is thick, pitch of holes 600nm, aperture 1 μ m.The quartz plate that will be aforementioned deposit metal immerses in toluene solution and dissolves after template polystyrene microsphere, and with deionized water washing, obtains the transparent electrode material of the Graphene that contains metallic aluminium and N doping.The front view of transparent electrode material and a left side (right side) view is as shown in A and B in Fig. 5.
The metal layer thickness of transparent electrode material is 3nm, and the metal level number of plies is 1 layer; Graphene thickness is 1.2nm, and the graphene layer number of plies is 1 layer.
The visible light transmissivity of transparent electrode material is 98%, infrared light transmitance 98%, square resistance 3 Ω/sq.
Embodiment 3
The present embodiment is the preparation method for b type transparent electrode material of the present invention is described.
(1) preparation of Graphene colloidal sol: dissolve 600mg sodium borohydride in 15g water, the sodium borohydride solution obtaining is added in the graphene oxide colloidal sol obtaining in 50mL preparation example 1, by the sodium carbonate liquor regulator solution pH value to 9 of 5 % by weight, these mixtures are stirred to 1h at 80 DEG C, then use deionized water centrifuge washing 5 times under the rotating speed of 5000rpm, Graphene after washing is dissolved in the water and alcohol mixed solution of 1: 1, and obtaining concentration is the Graphene colloidal sol of 10mg/mL.
(2) preparation of graphene film: adopt dip-coating method, by pet film PET (Japanese Ai Ke AICA, model HC2106, size is 2cm × 2cm, thickness 0.188mm) immerse in the Graphene colloidal sol that obtains of step (1), then with the direction vertical with horizontal plane, PET is at the uniform velocity lifted out to liquid level, with the unnecessary Graphene colloidal sol in the deionized water washing PET back side, under room temperature, dry, obtain graphene layer, thickness is 7nm.
(3) method of ultraviolet photolithographic is prepared photoresist template: the method that adopts ultraviolet photolithographic, on the graphene layer first obtaining in step (2), use the spin coating instrument spin coating 5mL photoresist (ALLRESIST of company, model AR-N4340), then in darkroom, on photoresist, place template (buying the semiconducter research institute in the Chinese Academy of Sciences) uv-exposure with vertical nano-wire lattice, obtain template nanowire mesh grid pattern in the lower photoetching agent pattern etching of developer solution (ALLRESIST producer, model AR300-26) effect.Under ESEM, detect, the width of photoresist nano wire is 2 μ m, distance between centers of tracks 20 μ m.
(4) evaporation Cu in photoresist space: by the method for hot evaporation, with Cu target evaporation 10s on above-mentioned PET sheet, obtain the Cu that 3nm is thick in photoresist gap.Wash away photoresist by developing solution dissolution, then use deionized water cyclic washing 3 times, obtain the transparent electrode material that contains metal Cu and Graphene.
(5) transparent electrode material step (4) being obtained repeats abovementioned steps (1) and (2), prepares one deck graphene film on Cu transparent membrane again, obtains the transparent electrode material of double-layer graphite alkene.The front view of transparent electrode material and a left side (right side) view is as shown in A and B in Fig. 6.
The metal layer thickness of transparent electrode material is 3nm, and the metal level number of plies is 1 layer; Graphene thickness is 1.2nm; The Graphene number of plies is 2 layers.
The visible light transmissivity of transparent electrode material is 70%, infrared light transmitance 70%, square resistance 0.001 Ω/sq.By above-mentioned transparent electrode material bending 1000 times and each all bending in 90 ° after, visible light transmissivity is 70%, infrared light transmitance 70%, square resistance 0.001 Ω/sq.
Embodiment 4
The present embodiment is the preparation method for a type transparent electrode material of the present invention is described.
(1) preparation of Graphene colloidal sol: consistent with the step (1) of embodiment 3, obtaining concentration is the Graphene colloidal sol of 10mg/mL, with deionized water dilution, obtains the rare colloidal sol of 0.1mg/mL graphite.
(2) preparation of Ag nano wire and Graphene mixed sols: will singly disperse Ag nano wire (according to Scalable Coating and Properties of Transparent such as document Yi Cui, Flexible, SilverNanowire Electrodes, ACS NANO, 2010,4 (5): the method preparation in 2955-2963, grain diameter 40nm-100nm, the rare colloidal sol of 0.1mg/mL graphite 2mg/mL) obtaining with step (1) mixes, volume mixture ratio 1: 1.Ultrasonic 30 minutes (ultrasonic power 20kW);
(3) preparation of Ag nano wire and Graphene mixed film: use the method for blade coating to use glass bar blade coating to PET (Japanese Ai Ke AICA 1mL mixed sols, model HC2106, size is 2cm × 2cm, thickness 0.188mm) go up and dry, obtain transparent electrode material.The front view of transparent electrode material and a left side (right side) view is as shown in A and B in Fig. 7.
The metal A g of transparent electrode material and Graphene mixed layer thickness are 3nm, and metal and the Graphene mixed layer number of plies are 1 layer.
The visible light transmissivity of transparent electrode material is 92%, infrared light transmitance is 92%, square resistance is 100 Ω/sq.By above-mentioned transparent electrode material bending 1000 times and each all bending in 90 ° after, visible light transmissivity is 92%, infrared light transmitance 92%, square resistance recruitment are less than 5%.
Claims (10)
1. a transparent electrode material, it is characterized in that, this material comprises substrate and is attached to this on-chip conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region
Wherein, described conductive layer is formed by the mixture layer of Graphene and metal, the weight ratio of described Graphene and metal is 1:0.01-10000, and the number of plies of the mixture layer of described Graphene and metal is 1-20 layer, and the thickness of the mixture layer of Graphene and metal is 0.2-300nm described in every one deck; Or
Described conductive layer is alternately formed by graphene layer and metal level, and the thickness of described graphene layer is 0.2-10nm, and the number of plies of described graphene layer is 1-10 layer, the thickness of described metal level is 0.2-300nm, the number of plies of described metal level is 1-10 layer, wherein, and the metal film that described metal level is patterning.
2. transparent electrode material according to claim 1, wherein, described metal is to be selected from one or more in silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium.
3. transparent electrode material according to claim 1, wherein, described substrate be 90-100% at the light transmittance of visible region, one or more in be 90-100% at the light transmittance of infrared light region glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and polyacrylate film.
4. the preparation method by the transparent electrode material described in any one in claim 1-3, it is characterized in that, the method comprises, on substrate, form conductive layer, this conductive layer contains Graphene and metal, the square resistance of described conductive layer is 0.001-1000 Ω/sq, and described conductive layer is 70-98% at the light transmittance of visible region, is 70-98% at the light transmittance of infrared light region.
5. method according to claim 4, wherein, the described method that forms conductive layer on substrate comprises, the dispersion liquid that contains Graphene and metal is attached to substrate surface, at 60-200 DEG C, place after 1-120 minute, then repeat following steps 0-19 time: the dispersion liquid that contains Graphene and metal is attached to the surface of the mixture layer of obtained Graphene and metal, at 60-200 DEG C, places 1-120 minute.
6. method according to claim 5, wherein, described in contain Graphene and metal dispersion liquid in the concentration of Graphene be 0.001-10mg/mL, the concentration of metal is 0.01-100mg/mL.
7. according to the method described in any one in claim 5-6, wherein, the consumption of the dispersion liquid that every one deck contains Graphene and metal is that the thickness of the mixture layer that contains Graphene and metal described in every one deck in the transparent electrode material that makes to obtain is 0.2-300nm.
8. method according to claim 4, wherein, the described method that forms conductive layer on substrate comprises, alternately forms metal level and graphene layer on substrate.
9. method according to claim 8, wherein, the thickness of described metal level is 0.2-300nm, and the number of plies of described metal level is 1-10 layer, and the thickness of described graphene layer is 0.2-10nm, and the number of plies of described graphene layer is 1-10 layer.
10. according to the method described in any one in claim 5-6,8 and 9, wherein, described metal is to be selected from one or more in silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, and described substrate is is 90-100% at the light transmittance of visible region, one or more in be 90-100% at the light transmittance of infrared light region glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and polyacrylate film.
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| CN102881841B (en) * | 2012-10-16 | 2016-01-20 | 北京大学 | With the semiconductor photoelectric device that copper/graphene combination electrode is anode |
| CN102982861A (en) * | 2012-11-27 | 2013-03-20 | 无锡力合光电石墨烯应用研发中心有限公司 | Transparent conductive film layer for capacitive touch screen |
| CN103019493A (en) * | 2012-12-24 | 2013-04-03 | 无锡力合光电石墨烯应用研发中心有限公司 | Electrode structure for capacitive touch screens and preparation method thereof |
| CN103227241A (en) * | 2013-04-10 | 2013-07-31 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of double-faced crystalline silicon solar cell |
| CN104183700A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Flexible transparent conductive graphene film and manufacturing method and application thereof |
| CN103325442B (en) * | 2013-06-27 | 2015-11-11 | 北京印刷学院 | A kind of compound transparent electricity conductive film and preparation method thereof |
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| WO2017210819A1 (en) * | 2016-06-06 | 2017-12-14 | 孙英 | Novel electrically conductive graphite material |
| CN106037735A (en) * | 2016-07-07 | 2016-10-26 | 苏州海神联合医疗器械有限公司 | High-conductivity electrode applicable to electromyography-evoked potential equipment |
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| CN106684114B (en) * | 2017-01-04 | 2019-10-18 | 武汉华星光电技术有限公司 | Flexible display device and preparation method thereof |
| US11511999B2 (en) | 2017-06-15 | 2022-11-29 | Tata Steel Limited and Centre for Nano | Process for producing graphene based transparent conductive electrode and the product thereof |
| CN107265880B (en) * | 2017-06-26 | 2020-01-03 | 信利光电股份有限公司 | Anti-dazzle glass coating method |
| CN107610814B (en) * | 2017-08-30 | 2020-08-11 | 中国科学院宁波材料技术与工程研究所 | Transparent electrode based on ultrathin metal grid and preparation method thereof |
| CN109524481A (en) * | 2017-09-20 | 2019-03-26 | 上海太阳能工程技术研究中心有限公司 | A kind of highly conductive electrode of solar battery of low cost and preparation method thereof |
| CN108727068B (en) * | 2018-07-03 | 2021-04-13 | 句容市博远电子有限公司 | Preparation method of thin NTC thermistor |
| CN109763178B (en) * | 2019-03-15 | 2023-04-25 | 东华大学 | Combined auxiliary electrode for internal conical surface electrostatic spinning nozzle |
| CN110123310A (en) * | 2019-04-19 | 2019-08-16 | 东北大学 | Domain type flexible combination electrocardioelectrode |
| CN110429087A (en) * | 2019-06-27 | 2019-11-08 | 重庆惠科金渝光电科技有限公司 | Array substrate metal wire and preparation method thereof and display panel |
| CN112531119B (en) * | 2020-12-15 | 2022-08-30 | 中国华能集团清洁能源技术研究院有限公司 | Flexible transparent electrode and battery suitable for flexible photoelectric device and preparation method |
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