CN103794265A - Composite material of graphene and nanowires and preparation method thereof - Google Patents
Composite material of graphene and nanowires and preparation method thereof Download PDFInfo
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- CN103794265A CN103794265A CN201410066169.7A CN201410066169A CN103794265A CN 103794265 A CN103794265 A CN 103794265A CN 201410066169 A CN201410066169 A CN 201410066169A CN 103794265 A CN103794265 A CN 103794265A
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- graphene
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002070 nanowire Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- -1 pick Chemical compound 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010941 cobalt Substances 0.000 claims description 4
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010703 silicon Substances 0.000 claims description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010931 gold Substances 0.000 claims description 2
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention discloses a composite material of graphene and nanowires. The composite material of the graphene and the nanowires comprises a substrate and is characterized in that from inside to outside, at least one layer of the nanowires is arranged on the surface of the subsrate, and the graphene is arranged at the outermost layer. The composite material of the graphene and the nanowires adopts the nanowires for bridging, can well overcome the defects occurring when the graphene is transferred under the condition of not affecting the light-permeable property of the graphene, largely lowers sheet resistance of the graphene, avoids the problem of attenuation of the sheet resistance at high temperature and under irradiation of ultraviolet, and can also solve the problem that the sheet resistance weakens due to the fact that the composite material is exposed in air for a long time after being mixed with the graphene.
Description
Technical field
The invention belongs to field of nanometer material technology, be specifically related to composite material of a kind of Graphene and nano wire and preparation method thereof.
Background technology
Graphene be carbon atom by the monoatomic layer two dimensional crystal of the tightly packed one-tenth of hexagonal structure, except having the characteristics such as excellent optics, calorifics, mechanics, the charge carrier of Graphene shows the behavior that is similar to photon, intrinsic mobility can reach 2 × 10
5cm
2/ (VS) (J. Appl. Phys. 2011,109,093702.), the electrical properties of this excellence makes it in high-frequency electron device, have huge using value.In order to realize its potential application, primary problem is how to solve the defect occurring in the Graphene transfer of chemical vapour deposition technique growth, and this defect is mainly in transfer process and causes the sheet resistance of Graphene higher, affects the application of Graphene.The current defect common methods occurring in Graphene transfer that solves, has two kinds, and a kind of is the defect that the Graphene of method solution transfer by repeatedly shifting brings, but, the Graphene number of plies shifting is more, and light transmittance is just lower, has a strong impact on the effect of Graphene; The second reduces the rear higher defect of Graphene sheet resistance of transfer by Graphene is adulterated, although this method can significantly reduce the sheet resistance of Graphene, but doping effect is unstable, as high temperature, UV irradiation, or doping time is long, dopant may be reunited, decompose, or with airborne oxygen, reactions such as water vapour etc. and make sheet resistance decay, weatherability is poor.
Summary of the invention
The object of the invention is to overcome the problem occurring in existing Graphene transfer, composite material of a kind of Graphene and nano wire and preparation method thereof is provided.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose adopts:
A composite material for Graphene and nano wire, comprises substrate, and its feature is, from inside to outside, at least comprise one deck nano wire on the surface of substrate, and outermost layer is Graphene.
Further, Graphene and nano wire are alternately laminated.
Further, from inside to outside, be followed successively by nano wire and Graphene on the surface of substrate; Or be followed successively by Graphene, nano wire and Graphene; Or be followed successively by nano wire, Graphene, nano wire and Graphene.
Further, described nano wire is nanowires or semiconductor nanowires.
Further, described nanowires comprises at least one in copper, silver, cobalt, gold, nickel, zinc, iron, lead, aluminium, platinum, ruthenium, molybdenum, niobium, iridium, palladium, titanium, pick, tungsten, vanadium, bismuth and carbon, described semiconductor nanowires comprises potassium molybdate, sodium molybdate, titanium oxide, zinc oxide, tantalum oxide, molybdenum oxide, silicon, indium phosphide, gallium nitride, cuprous oxide, cupric oxide, carborundum, aluminium nitride, GaAs, indium arsenide, lithium vanadate, lead titanates, selenium, cobalt acid nickel, zinc sulphide, bismuth oxide, cobalt oxide, manganese oxide, gallium oxide, silver sulfide, cadmium sulfide, copper sulfide, cuprous sulfide, indium oxide, indium sulfide, tin oxide, bismuth telluride, cadmium telluride, manganese sulfide, tungsten oxide, bismuth telluride, vanadium oxide, iron oxide, cadmium selenide, germanium oxide, indium oxide, indium nitride, at least one in copper selenide and Berzeline.
Further, the diameter of described nano wire is 10 nm-800 nm.
Further, the length of described nano wire is 10 nm-1000 μ m.
Further, described substrate is polyphenyl dioctyl phthalate glycol ester, Merlon, polyvinyl chloride, polyethylene, PEN(PEN), glass or silicon chip.
The preparation method of the composite material of above-mentioned Graphene and nano wire, comprises basad surface transfer Graphene and coating nano wire, and its feature is, comprises the steps:
(1) at least basad surface-coated one deck nano wire;
And (2) making outermost layer is Graphene.
Further, basad surface is coated with successively nano wire and shifts Graphene;
Or shift successively Graphene, coating nano wire and shift Graphene;
Or be coated with successively nano wire, shift Graphene, be coated with nano wire and shift Graphene.
The transfer of Graphene can adopt PMMA transfer method, PDMS transfer method, heat to discharge adhesive tape transfer method, electrostatic film transfer method etc.
Nano wire be coated with immersion, blade coating, spin coating, spraying, roller coat, slot coated, nano impression, printing, transfer printing, silk screen printing and nick printing etc.
Nano wire water, ethanol, isopropyl alcohol, nitrogen methyl pyrrolidone or water-base resin are mixed with to the coating fluid that concentration is 1-100mg/mL.
After coating, need to be dried nano wire, except natural drying, can also accelerate by baking the dry run of nano wire, baking temperature is 50-300 ℃, and baking time is 1-200 min.
The present invention adopts the compound method of Graphene and nano wire, and utilizing nano wire to put up a bridge can be in the situation that affecting Graphene light transmission, well solves the defect problem occurring in Graphene transfer, reduces greatly the sheet resistance of Graphene; In addition, the complex method effect of this nano wire and Graphene is better, high temperature, UV irradiation, or the long problem that all there will not be sheet resistance decay of doping time.Adopt stepped construction of the present invention can solve the material such as dopant or nano wire and be exposed in air, with airborne oxygen, sulphur, reactions such as water vapour and make the problem of sheet resistance decay.So, adopt the present invention in substrate, particularly in flexible substrates, to develop visible light transmittance rate high, sheet resistance is little, mist degree is low, the conductive film having an even surface, the conductive film that stability is good, at touch-screen, flexible display, e-book, antistatic film, electromagnetic shielding, the fields such as solar cell have huge using value.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is not construed as limiting the invention.
Fig. 1 is the embodiment of the present invention 1 preparation flow schematic diagram;
Fig. 2 is the embodiment of the present invention 3 preparation flow schematic diagrames, wherein, and 1-Graphene, 2-growth substrate, 3-target substrate, 4-nano wire.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, preferred embodiment described herein only, for description and interpretation the present invention, is not intended to limit the present invention.
A composite material for Graphene and nano silver wire, as shown in Figure 1, detailed process is as follows for preparation flow:
(1) transfer of Graphene (PDMS method shift): at the copper foil surface continuous graphene film (this process has very many introductions in the prior art, exceeds narration at this) of growing, have the Copper Foil of Graphene to flatten by growing with vapour deposition process;
PDMS film is attached to the graphene layer surface being grown on Copper Foil, then puts into the mixed solution of hydrochloric acid and hydrogen peroxide, erode growth substrates copper, put into deionized water and wash away the foreign ion of Graphene adsorption.From deionized water, take out, nitrogen gun is blown away deionized water, and 80 ℃ of baking 10min remove the hydrone on Graphene surface, obtain PDMS/ Graphene, PDMS/ Graphene and PET(polyester film) laminating, 90 ℃ of baking 15 min, obtain PET/ Graphene after removing PDMS;
(2) coating of nano silver wire (adopting the technology of slot coated): by nano silver wire (Ag-NW) aqueous isopropanol, concentration: 20mg/ml, diameter: 20nm, length: 30 μ m, be coated on the surface (Graphene side) of PET/ Graphene, 80 ℃ of baking 150min, obtain PET/ Graphene/Ag-NW;
The transfer of outermost layer Graphene: by the method for PDMS, Graphene is transferred to PET/ Graphene/Ag-NW upper, obtaining structure is the composite material of PET/ Graphene/Ag-NW/ Graphene.
The composite material obtaining sheet resistance average 20.6 Ω/sq, light transmittance average is 87%, mist degree average 0.9% is placed after 30 days sheet resistance average 20.6 Ω/sq, light transmittance average 87%, mist degree average 0.9%.
Contrast:
Adopt above-mentioned identical method first on PET, to shift two layer graphenes, then on Graphene, be coated with one deck nano silver wire (condition is the same), obtain PET/ Graphene/Graphene/nano silver wire, sheet resistance average 22.5 Ω/sq, light transmittance average 87%, mist degree average 0.9%, place after 30 days, sheet resistance average 100.7 Ω/sq, light transmittance average 86.6%, mist degree average 1.1%.
Can find out, take Graphene as outermost layer, can obviously improve the weatherability of composite material, place after 30 days, sheet resistance does not decay substantially, properties is stable, and when nano silver wire is exposed to outermost, nano silver wire easily produces chemical reaction with airborne sulphur (S), cause sheet resistance obviously to decay to 100.7 Ω/sq by 22.5 Ω/sq, light transmittance reduces, and mist degree also increases to some extent.
A composite material for Graphene and copper nano-wire, as shown in Figure 1, detailed process is as follows for preparation flow:
(1) transfer of Graphene (transfer method of PMMA, prior art are exceeded narration): at the copper foil surface continuous graphene film of growing, adopt the method for PMMA and Graphene is transferred on glass with vapour deposition process;
(2) coating of copper nano-wire (adopting the technology of spraying): by the aqueous solution of copper nano-wire (Cu-NW) (concentration: 100mg/ml, diameter: 100 nm, length: 100 μ m are sprayed on the surface (Graphene side) of glass/Graphene, 300 ℃ of baking 5min of temperature;
Repeating step (1), obtains the composite material that structure is glass/Graphene/Cu-NW/ Graphene.
The sheet resistance average of the composite material obtaining is 55.2 Ω/sq, and light transmittance average is 86.8%, and mist degree average is 1.05%.Place after 30 days sheet resistance average 55.2 Ω/sq, light transmittance average 86.8%, mist degree average 1.05%.
Contrast:
Adopt above-mentioned identical method first at continuous transfer two layer graphenes on glass, then on Graphene, spray layer of copper nano wire (condition is the same).Obtain PET/ Graphene/Graphene/Cu-NW, sheet resistance average 57.6 Ω/sq, light transmittance average is 86.5%, mist degree 1.07%.Place after 30 days sheet resistance average 121.5 Ω/sq, light transmittance average 85.6%, mist degree average 1.32%.Can find out, take Graphene as outermost layer, can obviously improve the weatherability of composite material, and when copper nano-wire is exposed to outermost, copper nano-wire easily produces chemical reaction with airborne carbon dioxide steam etc., causes degradation.
A composite material for Graphene and Pb Nanowires, as shown in Figure 2, detailed process is as follows for preparation flow:
(1) by the method for transfer printing, Pb Nanowires (Pb-NW) is transferred in substrate of glass: take glass as target substrate, by the ethanolic solution of Pb Nanowires (Pb-NW) (5mg/L, diameter: 100nm, length: 50 μ m), filter, on filter membrane, form uniform conductive network.Using the filter membrane that has covered Pb Nanowires layer as transfer film, be pressed on glass, 150 ℃ baking 55min, remove filter membrane, obtain glass/Pb-NW;
(2) with PDMS transfer method (transfer process of PDMS method in reference example 1 step 1), Graphene is transferred to glass/Pb-NW, obtain glass/Pb-NW/ Graphene;
Repeating step (1) and (2), obtain the composite material of glass/Pb-NW/ Graphene/Pb-NW/ graphene-structured.
The sheet resistance average of gained glass/Pb-NW/ Graphene/Pb-NW/ graphene composite material is 11.5 Ω/sq, and light transmittance is 85.8%, mist degree 1.2%.
Contrast
Adopting above-mentioned identical method is glass/Pb-NW/ graphene composite material in the structure that obtains on glass.
The sheet resistance average of gained glass/Pb-NW/ graphene composite material is 30.2 Ω/sq, and light transmittance average is 86.8%, and mist degree average is 1.02%.Can find out, increase alternately laminated quantity, can obviously reduce the sheet resistance of material.
A composite material for Graphene and zinc oxide nanowire, as shown in Figure 2, detailed process is as follows for preparation flow:
(1) zinc oxide nanowire (ZnO-NW) coating (method of roller coat), by the solution of zinc oxide nanowire (ZnO-NW) (5mg/L, diameter: 100nm, length: 50 μ m) are rolled onto in quartz substrate, 150 ℃ of baking 55min, obtain quartz/ZnO-NW;
(2) Graphene shifts (by the method for PMMA): Graphene is transferred to quartz/ZnO-NW, obtain quartz/ZnO-NW/ Graphene;
Repeating step (1) and (2), obtain the composite material of quartz/ZnO-NW/ Graphene/ZnO-NW/ graphene-structured.
The sheet resistance average of gained quartz/ZnO-NW/ Graphene/ZnO-NW/ graphene composite material is 20.6 Ω/sq, and light transmittance average is 85.6%, and mist degree average is 1.24%.
Contrast
Adopting above-mentioned identical method first on quartz, to obtain structure is quartz/ZnO-NW/ graphene composite material.
The sheet resistance average of gained quartz/ZnO-NW/ graphene composite material is 30.2 Ω/sq, and light transmittance average is 86.8%, and mist degree average is 1.02%.Can find out, increase alternately laminated quantity, can obviously reduce the sheet resistance of material.
Finally it should be noted that, the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a composite material for Graphene and nano wire, comprises substrate, and its spy is characterised in that, from inside to outside, at least comprise one deck nano wire on the surface of substrate, and outermost layer is Graphene.
2. the composite material of Graphene and nano wire according to claim 1, its spy is characterised in that, Graphene and nano wire are alternately laminated.
3. according to the composite material of Graphene described in claim 1 or 2 and nano wire, its spy is characterised in that, from inside to outside, is followed successively by nano wire and Graphene on the surface of substrate; Or be followed successively by Graphene, nano wire and Graphene; Or be followed successively by nano wire, Graphene, nano wire and Graphene.
4. according to the composite material of Graphene described in claim 1 or 2 and nano wire, its spy is characterised in that, described nano wire is nanowires or semiconductor nanowires.
5. the composite material of Graphene and nano wire according to claim 4, its spy is characterised in that, described nanowires comprises at least one in copper, silver, cobalt, gold, nickel, zinc, iron, platinum, ruthenium, molybdenum, niobium, iridium, palladium, titanium, pick, tungsten, vanadium, bismuth and carbon, described semiconductor nanowires comprises potassium molybdate, sodium molybdate, titanium oxide, zinc oxide, tantalum oxide, molybdenum oxide, silicon, indium phosphide, gallium nitride, cuprous oxide, cupric oxide, carborundum, aluminium nitride, GaAs, indium arsenide, lithium vanadate, lead titanates, selenium, cobalt acid nickel, zinc sulphide, bismuth oxide, cobalt oxide, manganese oxide, gallium oxide, silver sulfide, cadmium sulfide, copper sulfide, cuprous sulfide, indium oxide, indium sulfide, tin oxide, bismuth telluride, cadmium telluride, manganese sulfide, tungsten oxide, bismuth telluride, vanadium oxide, iron oxide, cadmium selenide, germanium oxide, indium oxide, indium nitride, at least one in copper selenide and Berzeline.
6. according to the composite material of Graphene described in claim 1 or 2 and nano wire, its spy is characterised in that, described substrate is polyphenyl dioctyl phthalate glycol ester, Merlon, polyvinyl chloride, polyethylene, PEN, quartz, glass or silicon chip.
7. the preparation method of the composite material of Graphene and nano wire described in claim 1, comprises basad surface transfer Graphene and coating nano wire, it is characterized in that, comprising:
(1) at least basad surface-coated one deck nano wire;
And (2) making outermost layer is Graphene.
8. the preparation method of the composite material of Graphene and nano wire according to claim 7, is characterized in that: basad surface is coated with successively nano wire and shifts Graphene; Or shift successively Graphene, coating nano wire and shift Graphene; Or be coated with successively nano wire, shift Graphene, be coated with nano wire and shift Graphene.
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