CN102569432A - Transparent electrode material and preparation method thereof - Google Patents
Transparent electrode material and preparation method thereof Download PDFInfo
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- CN102569432A CN102569432A CN2010105933064A CN201010593306A CN102569432A CN 102569432 A CN102569432 A CN 102569432A CN 2010105933064 A CN2010105933064 A CN 2010105933064A CN 201010593306 A CN201010593306 A CN 201010593306A CN 102569432 A CN102569432 A CN 102569432A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- 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, photoelectric devices such as solar cell, semiconductor detector, electroluminescence and flat-panel monitor all need the transparency electrode of low resistance, high light transmittance ability.And flexible optoelectronic device of new generation more needs resistant to bending transparency conductive electrode on this basis.Transparent conductive oxide film (TCOs), metal film, CNT and Graphene are usually as the transparency electrode of above-mentioned device.ITO (tin-doped indium oxide) as indium oxide system among the TCOs is widely used.But there are many deficiencies in ITO; For example: metals such as relative Ag, Ni; The resistivity of ITO is higher can not to satisfy the more demand for development of low-resistivity of above-mentioned device, and the scarcity of indium reserves makes involving great expense of ITO, and ITO is unstable on flexible substrates; Not anti-bending is so hope to develop its substitution material.The CNT light transmittance only is superior to ITO at infrared region.Under the state-of-the-art, graphene conductive property 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 objective of the invention is in order to overcome existing transparent electrode material transmitance low; Resistivity is higher; Lack flexible and the shortcoming of anti-deflection not, provide a kind of transmitance high, conduct electricity very well transparent electrode material that metal film that pliability is excellent and Graphene are compound and preparation method thereof.
The present invention provides a kind of transparent electrode material; Said transparent electrode material comprises substrate and attached to this on-chip conductive layer; This conductive layer contains Graphene and metal; The square resistance of said conductive layer is 0.001-1000 Ω/sq, and the light transmittance in the visible region of said 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; This method comprises; On substrate, form conductive layer, this conductive layer contains Graphene and metal, and the square resistance of said conductive layer is 0.001-1000 Ω/sq; The light transmittance of said conductive layer in the visible region is 70-98%, is 70-98% at the light transmittance of infrared light region.
Transparency electrode of the present invention is because contain the composite construction of metal and Graphene; Make it not only have high light transmittance, low-resistance excellent properties; And because the structural stability and the resistance to bend(ing) of transparency electrode have been strengthened in the adding of Graphene; Thereby further increased electron propagation ducts, finally improved 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 the electron bridge beam action after compound with metal film, further increase the conductivity of metal film; And Graphene is all very high in ultraviolet, visible light, infrared light district transmitance, can not influence the light transmission of metal film.
Transparent electrode material of the present invention is at photoelectric device, photodetector and semiconductor light emitting, and is especially of many uses aspect flexible devices such as flexible solar battery, flexible display.Preparation method's of the present invention technology is simple, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the sketch map of a type transparent electrode material.
Fig. 2 is the sketch map of b type transparent electrode material.
Fig. 3 is the sketch map of another kind of b type transparent electrode material.
Fig. 4-the 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 that the mixture by Graphene and metal forms.
Embodiment
The present invention provides a kind of transparent electrode material; This material comprises substrate and attached to this on-chip conductive layer; This conductive layer contains Graphene and metal; The square resistance of said conductive layer is 0.001-1000 Ω/sq, and the light transmittance in the visible region of said conductive layer is 70-98%, is 70-98% at the light transmittance of infrared light region; Under the preferable case, the square resistance of said conductive layer is 0.001-100 Ω/sq, and the light transmittance in the visible region of said conductive layer is 80-98%, is 80-98% at the light transmittance of infrared light region.
And resistance descends less than 2% transparent electrode material of the present invention in bending 1000 times on the flexible substrate and after all bending to 90 ° at every turn.
In transparent electrode material of the present invention; Said conductive layer can be formed by the mixture layer of Graphene and metal; At this moment; The weight ratio of said Graphene and metal can be 1: 0.01-10000, and the number of plies of the mixture layer of said Graphene and metal can be the 1-20 layer, the thickness of the mixture layer of said Graphene of each layer and metal can be 0.2-300nm; In order to obtain better light transmission and flexible, under the preferable case, the weight ratio of said Graphene and metal is preferably 1: 0.1-1000, the thickness of the mixture layer of said Graphene of each layer and metal is preferably 0.2-100nm.
Under the preferable case; Said conductive layer in the transparent electrode material of the present invention also can be formed by graphene layer and replacing property of metal level; The thickness of said graphene layer can be 0.2-10nm; The number of plies of said graphene layer can be the 1-10 layer, and said metal layer thickness can be 0.2-300nm, and the number of plies of said metal level can be the 1-10 layer.In order to obtain better light transmittance and flexible, under the preferable case, the thickness of said graphene layer is 0.2-3nm, and the number of plies of said graphene layer can be the 1-2 layer; Said metal layer thickness is 0.5-10nm, and the number of plies of said metal level can be the 1-2 layer.It should be explicitly made clear at this point that above-mentioned thickness refers to the average thickness of graphene layer and metal level respectively.
Under the preferable case; Said metal level among the present invention is the metal film of patterning, said metal film be preferably the discontinuous metal film that is selected from the continuous metal film formed by the micro-nano becket, forms by the micro-nano becket, by regular hole arrange the two-dimensional metallic microgrid that forms, a kind of in the two-dimensional metallic microgrid that forms by the arrangement of irregular hole, the metal film of forming by the continuous metal island, the metal film of forming by discontinuous metal island and the metal film formed by one-dimensional metal nm line.In order to obtain better conductivity, light transmission and flexible further is preferably by regular hole and arranges the two-dimensional metallic microgrid that forms.
In transparent electrode material of the present invention, said metal can be preferably gold or silver for being selected from silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and the titanium one or more.
Graphene related among the present invention can be the conventional various Graphenes that use in this area; The present invention does not have specific (special) requirements to the number of plies of said Graphene; Can be the mixture of single-layer graphene and multi-layer graphene; The Graphene of said multilayer is generally the multi-layer graphene of 2-10 layer, and in addition, said Graphene is for the Graphene all be made up of carbon atom or be doped with heteroatomic Graphene.Wherein, the said hetero-atom that is doped with in the heteroatomic Graphene can be selected from one or more in nitrogen, oxygen, sulphur, boron and the phosphorus.
In the present invention; Can select different substrates according to different demands; In transparent electrode material of the present invention; Said substrate can be 90-100% for the light transmittance in the visible region; Be preferably 92-98%, be 90-100% at the light transmittance of infrared light region, be preferably in transparent polymeric film, glass and the quartz of 92-98% one or more, said transparent polymeric film can be in polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and the polyacrylate film one or more.
Conductive layer on the 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 that the elder generation that replaces forms graphene layer, forms metal level again, also has a kind of elder generation's formation metal level for replacing; Form graphene layer again, according to the preparation method can both be divided into one type with the back.
Therefore, the present invention is directed to dissimilar conductive layers, two kinds of corresponding preparation method 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; This method comprises; Form conductive layer at substrate, said conductive layer is formed by the mixture layer of Graphene and metal, and the square resistance of the said conductive layer of formation is 0.001-1000 Ω/sq; The light transmittance of said conductive layer in the visible region is 70-98%, is 70-98% at the light transmittance of infrared light region.
The present invention does not have specific (special) requirements to the said method that on substrate, forms conductive layer; For example can carry out as follows: the dispersion liquid that will contain Graphene and metal is attached to substrate surface; After 60-200 ℃ of held 1-120 minute; Further be preferably at 80-120 ℃ of held 20-40min, place 2-10min at 140-160 ℃ then, repeat following steps then 0-19 time: will contain the surface of the dispersion liquid of Graphene and metal attached to the mixture layer of resulting Graphene and metal; After 60-200 ℃ of held 1-120 minute; Obtain having the transparent electrode material of conductive layer, further be preferably, place 2-10min at 140-160 ℃ then at 80-120 ℃ of held 20-40min.Wherein, repeat step and can determine whether as required to carry out, and the number of times that carries out, through above-mentioned steps, can on transparent substrates, form the conductive layer of 1-20 layer.
In above-mentioned preparation method, the concentration of the Graphene in the said dispersion liquid that contains Graphene and metal can be 0.001-10mg/mL, and concentration of metal can be 0.01-100mg/mL; Operation for ease, the concentration of Graphene is preferably 0.01-1mg/mL in the said dispersion liquid that contains Graphene and metal, and concentration of metal is preferably 0.1-10mg/mL.
Under the preferable case, the consumption that contains the dispersion liquid of Graphene and metal each time is to make that the said thickness that contains the mixture layer of Graphene and metal of each layer is 0.2-300nm in the transparent electrode material of acquisition.
In the present invention, will be called a type transparent electrode material through the transparent electrode material of this method preparation.As shown in Figure 1, wherein, 1 is substrate; 4 is the conductive layer that the mixture by Graphene and metal forms; 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 more on the conductive layer that conductive layer that the mixture by Graphene and metal forms can form at the mixture by Graphene and metal and form successively.
In above-mentioned preparation method; The dispersion liquid that will contain Graphene and metal does not have special qualification attached to the transparent substrates surface or attached to the method on the surface of the mixture layer of resulting Graphene and metal; For example can be preferably spin-coating method for being selected from spin-coating method, spraying process, knife coating and the infusion process one or more.
According to the method for the invention, the dispersion liquid of said Graphene and metal can provide with various forms, solation for example, and the said dispersion liquid that contains Graphene and metal can prepare with reference to prior art, and the present invention does not have specific (special) requirements, repeats no more at this.
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; This method comprises; On substrate, alternately form metal level and graphene layer, on substrate, to form conductive layer, the square resistance of said conductive layer is 0.001-1000 Ω/sq; The light transmittance of said conductive layer in the visible region is 70-98%, 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, and is comprising the transparent electrode material that after forming graphene layer earlier on the substrate, forms metal level, as shown in Figure 2; Wherein, 1 is substrate; 2 is metal level; 3 is graphene layer; With the transparent electrode material that after forming metal level earlier on the substrate, forms graphene layer, as shown in Figure 3, wherein, 1 is substrate; 2 is metal level; 3 is graphene layer.Fig. 2 and Fig. 3 just illustrate the two-layer transparent electrode material in two kinds of execution modes of the present invention respectively, one skilled in the art may determine that more graphene layer or metal level can form on metal level and graphene layer successively.
According to the method for the invention, under the preferable case, said metal layer thickness can be 0.2-300nm, is preferably 0.5-10nm, and the number of plies of said metal level can be the 1-10 layer, is preferably the 1-2 layer; The thickness of said graphene layer can be 0.2-10nm, is preferably 0.2-3nm; The number of plies of said graphene layer can be the 1-10 layer, is preferably the 1-2 layer.
In above-mentioned preparation method, the method for said formation graphene layer there is not special qualification, can carry out with reference to prior art, for example can be preferably spin-coating method for being selected from spin-coating method, spraying process, knife coating, infusion process or czochralski method; Method to said formation metal level does not have special qualification yet; For example can be preferably template for being selected from template, electric weaving method, stamped method, self-assembly method, etching method, sedimentation, electromagnetic field guiding method, sputtering method, sol-gal process, spin-coating method, spraying process, electrostatic spinning or knife coating.
Since in preparation method of the present invention employed metal, substrate and constitute the said Graphene of conductive layer and metal mixture layer, graphene layer thickness and kind etc. all with product in related identical, repeat no more at this.
Below in conjunction with embodiment the present invention is further specified.
In following examples, measure visible light transmissivity and infrared light transmitance with ultraviolet/visible/near infrared spectrometer (PerkinElmer Lambda950); (Guangzhou four point probe science and technology RTS-9) measures square resistance with two electrical measurement four point probe testers; Film thickness is with scanning probe microscopy test (DigitalInstruments Dimension 3100); With SEM ESEM (HIT, the HitachiS-4800) surface topography of test material, size (like average grain diameter etc.).
Preparation example 1
The preparation of graphene oxide colloidal sol
The natural flaky graphite (particle diameter is 200 μ m), the sodium nitrate of 5.0g and the potassium permanganate of 25.0g that in the concentration of 1500g is the concentrated sulfuric acid of 98 weight %, add 5.0g; The gained mixture after (promptly make the temperature of mixture is 0 ℃ through ice bath) under 0 ℃ the condition of ice bath stirred 5h, is then stirred 10h down at 30 ℃ again; In the gained mixture, adding 500mL water then dilutes; Then be warming up to 70 ℃ and stir 2h after; The concentration that adds 6mL is the hydrogen peroxide solution of 30 weight %, filters behind the stirring 1h, and then the filter cake that obtains being used concentration is the hydrochloric acid centrifuge washing of 10 weight %; Then use the deionized water centrifuge washing again; Gluey product after the washing is joined in the deionized water of 40mL, and ultrasonic dispersion obtains graphene oxide colloidal sol (content of graphene oxide is 20 weight %, and the content of water is 80 weight %) under the power of 200W.
Present embodiment is for the preparation method of b type transparent electrode material of the present invention is described.
(1) preparation 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 that provides in) preparation porous anodic aluminium oxide sheet, the aperture of measuring this porous anodic aluminium oxide sheet through ESEM is 50nm, pitch of holes is 150nm;
(2) electron beam evaporation plating metal level: deposited by electron beam evaporation appearance (Edwars, AUTO 500) is vapor deposition layer of metal silver on the anodic alumina film that step (1) obtains, 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) vapor deposition; Size is 2cm * 2cm; Thickness is 1mm); In concentration is 1% phosphoric acid solution, dissolve anodised aluminium, perforated metal silver grid natural subsidence is to quartz plate; With phosphoric acid unnecessary on the deionized water wash quartz plate and metal ion, 100 ℃ of following dry 4h;
(4) preparation graphene oxide film: on the quartz plate that metal grill is arranged that step (3) obtains with the graphene oxide colloidal sol of spin coating appearance to obtain in the thick preparation example 1 of rotating speed spin coating one deck 6nm of 4000rpm, 100 ℃ of dryings 10 minutes down;
(5) thermal reduction graphene oxide: under the Ar gas shiled; 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; With heating rate per hour 200 ℃ slowly be warmed up to 800 ℃ of heating 10 minutes, under the Ar gas shiled, in stove, slowly cool to room temperature then, reduction obtains containing the transparent electrode material of Graphene and argent.The front view of transparent electrode material and a left side (right side) view is shown in A and B among 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 the visible region light transmittance, infrared light district light transmittance is 92%, square resistance 5 Ω/sq.
Present embodiment is for the preparation method of b type transparent electrode material of the present invention is described.
(1) method of chemical vapour deposition (CVD) prepares nitrogen-doped graphene: with coating machine (section of section appearance technical development Co., Ltd among the KYUY; Model SBC-2); With Ni is target material, and sedimentation time 20s is in quartz plate (the magnificent quartzy electrical apparatus factory in Jinzhou; Size is 2cm * 2cm, and thickness is 1mm) the last thick Ni of hot vapor deposition 50nm.Quartz plate is put into quartz ampoule, and logical hydrogen (20sccm) and argon gas (100sccm) are when the body of heater central temperature is elevated to 800 ℃; Feed the CH4 of 60sccm and the NH3 of 60sccm, quartz ampoule is put into the body of heater center, after 10 minutes; With sample cool to room temperature under hydrogen stream; Obtain the graphene film that nitrogen mixes, using concentration is the Ni on 1% the phosphoric acid solution dissolving films, with surperficial three times of deionized water wash Graphene.
(2) preparation polystyrene microsphere: in the 500mL there-necked flask, add 10mL styrene and 150mL water, lead to nitrogen purge gas 15min, water bath with thermostatic control is stirred 20min down for 70 ℃, adds the 0.2g potassium peroxydisulfate, and 70 ℃ are reacted 24h down.Centrifugation obtains polystyrene microsphere list aqueous dispersion (phenylethylene micro ball concentration is 10 weight %, and the average grain diameter of phenylethylene micro ball is 1.3 μ m).
(3) be that template prepares the pattern metal film with the polystyrene microsphere monofilm: in 4.95mL polystyrene microsphere list aqueous dispersion (phenylethylene micro ball concentration is 10 weight %), add 0.05mL styrene and 5mL absolute ethyl alcohol; The sulfuric acid (concentration is 98%) that in this solution, adds 0.15 μ L again; Ultrasonic 15 minutes; Put into the quartz plate that there is graphene film on surface that above-mentioned steps (1) handles at container bottom, release the liquid in the container, with deionized water wash three times.(SENTECH ETCHCAB200), uses oxygen rie 10s, and the polystyrene microsphere particle diameter is reduced to 1 μ m with plasma etching (RIE) system.With magnetic control sputtering device (ULVAC Inc, ACS-400-C4), at operating pressure 0.5Pa, under the power 40W condition, vertical sputter 10s with quartz plate, plated metal Al in the polystyrene microsphere space obtains the thick Al of 3nm, pitch of holes 600nm, aperture 1 μ m.The aforementioned quartz plate that deposits metal is immersed in the toluene solution behind the dissolving template polystyrene microsphere, and use deionized water wash, obtain containing the transparent electrode material of the Graphene of metallic aluminium and N doping.The front view of transparent electrode material and a left side (right side) view is shown in A and B among 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.
Present embodiment is for the preparation method of b type transparent electrode material of the present invention is described.
(1) preparation of Graphene colloidal sol: dissolving 600mg sodium borohydride in the 15g water; The sodium borohydride solution that obtains is added in the graphene oxide colloidal sol that obtains in the 50mL preparation example 1; With the sodium carbonate liquor regulator solution pH value to 9 of 5 weight %, these mixtures are stirred down 1h at 80 ℃, use deionized water centrifuge washing 5 times under the rotating speed of 5000rpm then; Graphene after the washing is dissolved in 1: 1 the water and alcohol mixed solution, and obtaining concentration is the Graphene colloidal sol of 10mg/mL.
(2) preparation of graphene film: adopt dip-coating method, with pet film PET (Japanese Ai Ke AICA, model HC2106; Size is 2cm * 2cm, thickness 0.188mm) immerse in the Graphene colloidal sol that step (1) obtains, with the direction vertical PET is at the uniform velocity lifted out liquid level then with horizontal plane; With the unnecessary Graphene colloidal sol in the deionized water wash PET back side; Dry under the room temperature, obtain graphene layer, thickness is 7nm.
(3) method of ultraviolet photolithographic prepares the photoresist template: the method that adopts ultraviolet photolithographic; Earlier on the graphene layer that step (2) obtains with the spin coating appearance spin coating 5mL photoresist (ALLRESIST of company; Model AR-N4340); In the darkroom, on photoresist, place template (buying the semiconducter research institute in the Chinese Academy of Sciences) uv-exposure of band vertical nano-wire lattice then, photoresist patterning etching obtains template nano wire lattice under 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) vapor deposition Cu in the photoresist space:,, in the photoresist gap, obtain the thick Cu of 3nm with Cu target vapor deposition 10s on above-mentioned PET sheet with the method for hot vapor deposition.With dissolves flush away photoresist, use the deionized water cyclic washing again 3 times, obtain containing the transparent electrode material of metal Cu and Graphene.
(5) transparent electrode material that step (4) is obtained repeats abovementioned steps (1) and (2), on the Cu transparent membrane, prepares one deck graphene film 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 shown in A and B among 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.With above-mentioned transparent electrode material crooked 1000 times and all bend to 90 ° at every turn after, visible light transmissivity is 70%, infrared light transmitance 70%, square resistance 0.001 Ω/sq.
Present embodiment is for the preparation method of 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 the deionized water dilution, obtains the rare colloidal sol of 0.1mg/mL graphite.
(2) preparation of Ag nano wire and Graphene mixed sols: the single dispersion of general 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 among the 2955-2963, grain diameter 40nm-100nm; 2mg/mL) mix volume mixture ratio 1: 1 with the rare colloidal sol of 0.1mg/mL graphite that step (1) obtains.Ultrasonic 30 minutes (ultrasonic power 20kW);
(3) preparation of Ag nano wire and Graphene mixed film: with the method for blade coating the 1mL mixed sols is gone up and dried to PET (size is 2cm * 2cm, thickness 0.188mm for Japanese Ai Ke AICA, model HC2106) with the glass bar blade coating, obtain transparent electrode material.The front view of transparent electrode material and a left side (right side) view is shown in A and B among Fig. 7.
The metal A g of transparent electrode material and Graphene mixed layer thickness are 3nm, and the metal and the Graphene mixed layer number of plies are 1 layer.
The visible light transmissivity of transparent electrode material is 92%, the infrared light transmitance is 92%, square resistance is 100 Ω/sq.With above-mentioned transparent electrode material crooked 1000 times and all bend to 90 ° at every turn after, visible light transmissivity is 92%, infrared light transmitance 92%, square resistance recruitment be less than 5%.
Claims (13)
1. transparent electrode material; It is characterized in that; This material comprises substrate and attached to this on-chip conductive layer, this conductive layer contains Graphene and metal, and the square resistance of said conductive layer is 0.001-1000 Ω/sq; The light transmittance of said conductive layer in the visible region is 70-98%, is 70-98% at the light transmittance of infrared light region.
2. transparent electrode material according to claim 1; Wherein, Said conductive layer is formed by the mixture layer of Graphene and metal; The weight ratio of said Graphene and metal is 1: 0.01-10000, and the number of plies of the mixture layer of said Graphene and metal is the 1-20 layer, the thickness of the mixture layer of said Graphene of each layer and metal is 0.2-300nm.
3. transparent electrode material according to claim 1; Wherein, Said conductive layer is alternately formed by graphene layer and metal level, and the thickness of said graphene layer is 0.2-10nm, and the number of plies of said graphene layer is the 1-10 layer; Said metal layer thickness is 0.2-300nm, and the number of plies of said metal level is the 1-10 layer.
4. transparent electrode material according to claim 3, wherein, said metal level is the metal film of patterning.
5. transparent electrode material according to claim 1, wherein, said metal is to be selected from silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and the titanium one or more.
6. transparent electrode material according to claim 1; Wherein, said substrate is for being 90-100% at the light transmittance of visible region, being in glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and the polyacrylate film of 90-100% one or more at the light transmittance of infrared light region.
7. the preparation method of a transparent electrode material; It is characterized in that this method comprises, on substrate, forms conductive layer; This conductive layer contains Graphene and metal; The square resistance of said conductive layer is 0.001-1000 Ω/sq, and the light transmittance of said conductive layer in the visible region is 70-98%, is 70-98% at the light transmittance of infrared light region.
8. method according to claim 7; Wherein, The said method that on substrate, forms conductive layer comprises that the dispersion liquid that will contain Graphene and metal is attached to substrate surface, after 60-200 ℃ of held 1-120 minute; Repeat following steps then 0-19 time: will contain the surface of the dispersion liquid of Graphene and metal, at 60-200 ℃ of held 1-120 minute attached to the mixture layer of resulting Graphene and metal.
9. method according to claim 8, wherein, the concentration of the Graphene in the said dispersion liquid that contains Graphene and metal is 0.001-10mg/mL, concentration of metal is 0.01-100mg/mL.
10. according to any described method among the claim 7-9, wherein, the consumption that contains the dispersion liquid of Graphene and metal each time is to make that the said thickness that contains the mixture layer of Graphene and metal of each layer is 0.2-300nm in the transparent electrode material of acquisition.
11. method according to claim 7, wherein, the said method that on substrate, forms conductive layer comprises, on substrate, alternately forms metal level and graphene layer.
12. method according to claim 11, wherein, said metal layer thickness is 0.2-300nm, and the number of plies of said metal level is the 1-10 layer, and the thickness of said graphene layer is 0.2-10nm, and the number of plies of said graphene layer is the 1-10 layer.
13. according to any described method among the claim 7-9,11 and 12; Wherein, Said metal is to be selected from silver, copper, gold, aluminium, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and the titanium one or more, and said substrate is 90-100%, is in glass, quartz, polyvinyl alcohol film, polyimide film, polyester film, polychloroethylene film, polycarbonate membrane, polyurethane film and the polyacrylate film of 90-100% one or more at the light transmittance of infrared light region for the light transmittance in the visible region.
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| Publication number | Publication date |
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| CN102569432B (en) | 2014-12-10 |
| WO2012079360A1 (en) | 2012-06-21 |
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