CN105239061A - Graphene/metal composite thin film and preparation method thereof - Google Patents
Graphene/metal composite thin film and preparation method thereof Download PDFInfo
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- CN105239061A CN105239061A CN201510624104.4A CN201510624104A CN105239061A CN 105239061 A CN105239061 A CN 105239061A CN 201510624104 A CN201510624104 A CN 201510624104A CN 105239061 A CN105239061 A CN 105239061A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 199
- 239000010409 thin film Substances 0.000 title claims abstract description 84
- 239000002905 metal composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 113
- 238000006722 reduction reaction Methods 0.000 claims abstract description 18
- 239000010408 film Substances 0.000 claims description 157
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 49
- 239000010949 copper Substances 0.000 claims description 49
- 229910052802 copper Inorganic materials 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910021645 metal ion Inorganic materials 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000004831 Hot glue Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract 7
- 229910052737 gold Inorganic materials 0.000 description 37
- 239000010931 gold Substances 0.000 description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 18
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- -1 and wherein Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a preparation method for a graphene/metal composite thin film. The method comprises the following steps that (A) a growth substrate with a graphene thin film is immersed in a reduction solution to be subjected to an in-situ reduction reaction, and a metal particle/graphene thin film/growth substrate composite thin film is obtained; and (B) a metal particle/graphene thin film in the metal particle/graphene thin film/growth substrate composite thin film is transferred to a target substrate, and a target substrate/metal particle/graphene thin film composite thin film is obtained. According to the preparation method, metal particles are reduced to the graphene thin film in situ, a compositing process is omitted, and the metal particles well disperse on the graphene thin film, so that the sheet resistance of the graphene/metal composite thin film is lowered. The metal particles in the prepared graphene/metal composite thin film are clamped between the graphene thin film and the target substrate so as to be well protected, and therefore the time stability of the sheet resistance of the composite thin film is greatly enhanced.
Description
Technical field
The invention belongs to technical field of graphene, be specifically related to a kind of Graphene/metal composite thin film and preparation method thereof.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the planar material of honeycomb lattice, and be the two-dimensional material of single carbon atom thickness, its thickness is 0.334nm.Graphene, as its special pore texture of a kind of semi-metallic, determines it and has flexible feature.The inner carrier concentration of Graphene is up to 1013cm
-2, its theoretical mobility can reach 200000cm
2/ Vs, and the transmittance of single-layer graphene reaches 97.7%.These special performances of Graphene make it demonstrate wide application prospect in electronic information, energy novel material and war industry field.
Especially in transparent conductive film field, Graphene has excellent optics, mechanics and mechanical characteristics concurrently and becomes best transparent conductive film equivalent material of future generation.But at present Graphene also exists the higher problem of impedance, strongly limit its application in transparent conductive film field.Conventional method by the method for doping, electroconductibility is improved further, but its performance boost is also more limited.And the good electric conductivity of metallic substance can be utilized to carry out the defect of crane span structure graphene film by the compound of Graphene and metal, thus significantly promote the conductive characteristic of graphene film.
Current Graphene and metal composite prepare Graphene/metal composite thin film, need by being coated on by metal Nano structure on Graphene or substrate, and wherein, metal nanoparticle needs synthesis in addition, and flow process is complicated; And, metal nano ion is easily reunited when being coated with, thus increase the sheet resistance of Graphene/metal composite thin film, and the time stability of sheet resistance is poor, and therefore finding a kind of Graphene/metal composite method be simple and easy to is break through the integral part of graphene film performance bottleneck.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Graphene/metal composite thin film and preparation method thereof, preparation method provided by the invention is simple, and the Graphene prepared/metal composite thin film sheet resistance is low, and possesses good time stability.
The invention provides a kind of preparation method of Graphene/metal composite thin film, comprise the following steps:
A) there is the growth substrate of graphene film to immerse in reduced liquid length and carry out reduction reaction, obtain the laminated film of metallics/graphene film/growth substrate;
B) metallics/graphene film in the laminated film of described metallics/graphene film/growth substrate is transferred to target substrate, obtains the Graphene/metal composite thin film of target substrate/metallics/graphene film.
Preferably, described growth substrate is selected from copper substrate or nickel substrate.
Preferably, the water-soluble metal salt in described reduced liquid is one or more in hydrochloro-auric acid, sodium chloraurate, Silver Nitrate, Platinic chloride, sodium platinichloride.
Preferably, the water-soluble metal salt in described reduced liquid is one or more in hydrochloro-auric acid, Platinic chloride.
Preferably, in described reduced liquid, the concentration of metal ion is 0.001mg/L ~ 1g/L.
Preferably, in described reduced liquid, the concentration of metal ion is 0.01mg/L ~ 0.5g/L.
Preferably, in described reduced liquid, the concentration of metal ion is 0.05mg/L ~ 0.1g/L
Preferably, the time of reduction reaction is 10s ~ 24h.
Preferably, the time of described reduction reaction is 1min ~ 1h.
Preferably, described length has the growth substrate of graphene film to be prepared by the following method:
Growth substrate is put into Reaktionsofen, then in Reaktionsofen, passes into reactant gases and react, obtain the growth substrate with graphene film; Described reactant gases comprises hydrogen and gaseous carbon source.
Preferably, described target substrate is selected from PET, PE, PC, PVC, glass, silicon chip or quartz.
Preferably, described step B) be specially:
After adopting binding agent the laminated film of described metallics/graphene film/growth substrate and target substrate to be fitted, more described growth substrate is etched, obtain the Graphene/metal composite thin film of target substrate/metallics/graphene film.
Preferably in, described binding agent is selected from hot melt adhesive, UV light binding or polyester binding agent.
Preferably, the etching liquid of described etching is selected from ammonium persulphate.
Present invention also offers Graphene/metal composite thin film that a kind of above-mentioned preparation method prepares, sheet resistance is 170 ~ 250 Ω/.
Compared with prior art, the invention provides a kind of preparation method of Graphene/metal composite thin film, comprise the following steps: A) there is the immersion of the growth substrate of graphene film to carry out reduction reaction with in the reducing solution of metal ion by long, obtain the laminated film of metallics/graphene film/growth substrate; B) metallics/graphene film in the laminated film of described metallics/graphene film/growth substrate is transferred to target substrate, obtains the Graphene/metal composite thin film of target substrate/metallics/graphene film.The present invention has the growth substrate of graphene film to immerse with in the reducing solution of metal ion by long, Graphene and growth substrate and form galvanic cell system with the reducing solution of metal ion.Because the metallic element of described growing substrate is stronger than the reductibility of the metallic element of the metal ion in reduced liquid, therefore the metal ion in reduced liquid can be reduced into the metallics of nano-scale, metal-salt formed after being reduced into metal simple-substance stable, evenly, the metal-sol that floats on a liquid in single dispersion state.Under the mechanism of action of galvanic cell, the metal ion in described reduced liquid is very easily adsorbed on graphenic surface by after in-situ reducing, thus defines Graphene/metal composite thin film.This method saves complex flow and metallics can form good dispersion on graphene film, reduces the sheet resistance of Graphene/metal composite thin film.In the Graphene/metal composite thin film prepared, metallics is clipped between graphene film and target substrate, is well protected, and greatly strengthen the time stability of laminated film sheet resistance.
Result shows, the sheet resistance of Graphene/metal composite thin film provided by the invention is 170 ~ 250 Ω/, and it is very little described Graphene/metal composite thin film to be placed a month rear resistiveization.
Accompanying drawing explanation
Fig. 1 is the SEM figure of Graphene/metal composite thin film prepared by the embodiment of the present invention 2;
Fig. 2 is the SEM figure of Graphene/metal composite thin film prepared by the embodiment of the present invention 3;
Fig. 3 is the SEM figure of Graphene/metal composite thin film prepared by the embodiment of the present invention 4.
Embodiment
The invention provides a kind of preparation method of Graphene/metal composite thin film, comprise the following steps:
A) there is the growth substrate of graphene film to immerse in reduced liquid length and carry out reduction reaction, obtain the laminated film of metallics/graphene film/growth substrate;
B) metallics/graphene film in the laminated film of described metallics/graphene film/growth substrate is transferred to target substrate, obtains the Graphene/metal composite thin film of target substrate/metallics/graphene film.
First the present invention carries out reduction reaction by growing to have in the growth substrate of graphene film immersion reduced liquid, obtains the laminated film of metallics/graphene film/growth substrate.
In the present invention, described length has the growth substrate of graphene film to be prepared by the following method:
Growth substrate is put into Reaktionsofen, then in Reaktionsofen, passes into reactant gases and react, obtain the growth substrate with graphene film; Described reactant gases comprises hydrogen and gaseous carbon source.
Growth substrate is put into Reaktionsofen by the present invention, and wherein, described growth substrate is selected from Cu substrate or Ni substrate, is preferably Cu substrate.Described Reaktionsofen is preferably chemical vapor deposition stove.
After growth substrate is put into Reaktionsofen, in described Reaktionsofen, pass into reactant gases react.In the present invention, described reactant gases comprises hydrogen and gaseous carbon source, and wherein, described gaseous carbon source is selected from methane and/or ethene.In reactant gases, the volume ratio of described hydrogen and described gaseous carbon source is preferably 1 ~ 500:0.1 ~ 100, is more preferably 50 ~ 100:10 ~ 20.The temperature of described reaction is preferably 800 ~ 1200 DEG C, is more preferably 900 ~ 1100 DEG C, most preferably is 1000 ~ 1090 DEG C.The time of described reaction is preferably 1min ~ 60min, is more preferably 10min ~ 20min.
After reaction terminates, obtain the long growth substrate having graphene film.Described length there is the growth substrate of graphene film to immerse in reduced liquid and carry out reduction reaction, obtain the laminated film of metallics/graphene film/growth substrate.
In the present invention, described reduced liquid is the reduced liquid with metal ion, and the described reduced liquid with metal ion is configured by the following method:
Water-soluble metal salt is dissolved in deionized water, mixes, obtain the reduced liquid with metal ion.
In the present invention, water-soluble metal salt is preferably oxymuriate or nitrate.Be more preferably in hydrochloro-auric acid, sodium chloraurate, Silver Nitrate, Platinic chloride, sodium platinichloride one or more.Be more preferably in hydrochloro-auric acid, Platinic chloride one or more.The reductibility of the metal that described growth substrate is used is better than the reductibility of metal in described soluble metal compound, in described soluble metal compound, metal is preferably one or more in silver, platinum and gold, and namely described metal ion is preferably one or more in silver ions, platinum ion and gold ion.
Preferably, in described reduced liquid, the concentration of metal ion is 0.001mg/L ~ 1g/L; Preferred, in described reduced liquid, the concentration of metal ion is 0.01mg/L ~ 0.5g/L; Most preferred, in described reduced liquid, the concentration of metal ion is 0.05mg/L ~ 0.1g/L.
The described growth substrate with graphene film immersed in reduced liquid and carry out reduction reaction, the concrete grammar of the present invention to described reduction reaction does not have particular restriction, can carry out single sheet compound or volume to volume compound.
Wherein, described single sheet compound is carried out by the following method: the growth substrate with graphene film choosing single sheet; be soaked in the reduced liquid with metal ion; the grown substrate reduction of described metal ion; obtain difform metal nanoparticle or nano wire; separate out at graphene film surface crystallization, form the laminated film of metallics/graphene film/growth substrate.By the laminated film cleaning obtained, dry.The preferred of described reduction is 10s ~ 24h, is more preferably 1min ~ 1h.The method of the present invention to described cleaning, drying does not have particular restriction, well known to a person skilled in the art the method for cleaning, drying.In the present invention, described cleaning is preferably rinsed or rinsing, and described oven dry preferably uses air knife drying or oven for drying.
Described volume to volume compound is carried out by the following method: volume to volume is grown the length obtained has the growth substrate of graphene film to install, wherein, a part is soaked in the solution with metal ion with the growth substrate of graphene film, the grown substrate reduction of described metal ion, obtain difform metal nanoparticle or nano wire, separate out at graphene film surface crystallization, form the laminated film of metallics/graphene film/growth substrate, afterwards, volume to volume set composite starts, the air knife placed before rolling end, the solution that film surface is residual is used for blow off, by the laminated film rolling of metallics/graphene film/growth substrate obtained, with the growth substrate uncoiling of graphene film, continue above-mentioned reduction reaction, until obtain the laminated film of the metallics/graphene film/growth substrate of entire volume.The travelling speed of described volume to volume set composite is preferably 0.01m/min ~ 5m/min, is more preferably 0.1m/min ~ 1m/min.The preferred of described reduction is 10s ~ 24h, is more preferably 1min ~ 1h.
After obtaining the laminated film of metallics/graphene film/growth substrate, metallics/graphene film in the laminated film of described metallics/graphene film/growth substrate is transferred to target substrate, obtains the Graphene/metal composite thin film of target substrate/metallics/graphene film.
The method of the present invention to described transfer does not have particular restriction, preferably shifts by the following method:
After adopting binding agent the laminated film of described metallics/graphene film/growth substrate and target substrate to be fitted, more described growth substrate is etched, obtain the Graphene/metal composite thin film of target substrate/metallics/graphene film.
First, adopt binding agent the laminated film of described metallics/graphene film/growth substrate and target substrate to be fitted, in the present invention, described binding agent is selected from hot melt adhesive, UV light binding or polyester binding agent, is more preferably hot melt adhesive or UV light binding.Described target substrate is selected from PET, PE, PC, PVC, glass, silicon chip or quartz, is more preferably PET.
Then, described growth substrate etched, the present invention preferably adopts ammonium persulfate solution as etching liquid, and the concentration of described ammonium persulfate solution is preferably 5wt% ~ 20wt%, in embodiments more of the present invention, the concentration of described ammonium persulfate solution is 10wt%.
After growth substrate being etched, obtain Graphene/metal composite thin film, described Graphene/metal composite thin film is target substrate/metallics/graphene film three-layer composite structure.
Wherein, the laminated film of the metallics/graphene film/growth substrate of described entire volume completes the etch step of laminating with target substrate and growth substrate in volume to volume transfer device, obtains the Graphene/metal composite thin film of entire volume.
Present invention also offers Graphene/metal composite thin film that a kind of above-mentioned preparation method prepares.
Metal ion in-situ reducing on graphene film, is saved complex flow and metallics is uniformly dispersed on graphene film by the preparation method of Graphene/metal composite thin film provided by the present invention, reduces the sheet resistance of Graphene/metal composite thin film.In the Graphene/metal composite thin film prepared, metallics is clipped between graphene film and target substrate, is well protected, and greatly strengthen the time stability of laminated film sheet resistance.Result shows, the sheet resistance of Graphene/metal composite thin film provided by the invention is 170 ~ 250 Ω/, and it is very little described Graphene/metal composite thin film to be placed a month rear resistiveization.
In order to understand the present invention further, be described Graphene/metal composite thin film provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Chemical gas phase reaction stove is put in copper substrate, then in described chemical gas phase reaction stove, pass into hydrogen and methane gas, react under the condition of 1000 DEG C, obtain the copper substrate with graphene film, wherein, the volume ratio of described hydrogen and methane gas is 10:1.
Comparative example 1
1. the copper substrate with graphene film embodiment 1 prepared is under 110 DEG C of conditions, and hot melt adhesive, as binding agent, crosses roller and PET pressing.Form copper/Graphene/PET structure.
2. above-mentioned copper/Graphene/PET structure is put in the ammonium persulfate solution of 10wt% and etches.
3. after copper is etched completely, obtain the laminated film of PET/ Graphene, do with washed with de-ionized water after-blow.
4. measure the sheet resistance value of above-mentioned laminated film, sheet resistance scope is: 300 Ω/ ~ 350 Ω/.
Embodiment 2
1. prepare the chlorauric acid solution of 0.5g/L.
2. the 0.5g/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and leaves standstill the laminated film obtaining gold particle/graphene film/copper substrate for 1 minute and formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and PET pressing.Form PET/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PET/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PET/ gold particle/graphene film, do with washed with de-ionized water after-blow.
Described Graphene/metal composite thin film is carried out sem observation, the results are shown in Figure the SEM figure that 1, Fig. 1 is Graphene/metal composite thin film prepared by the embodiment of the present invention 2.As shown in Figure 1, gold grain is evenly distributed at graphenic surface.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 185 Ω/ ~ 210 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 190 Ω/ ~ 220 Ω/.
Embodiment 3:
1. prepare the chlorauric acid solution of 0.1g/L.
2. the 0.1g/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and leaves standstill the laminated film obtaining gold particle/graphene film/copper substrate for 10 minutes and formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and PET pressing.Form PET/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PET/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PET/ gold particle/graphene film, do with washed with de-ionized water after-blow.
Described Graphene/metal composite thin film is carried out sem observation, the results are shown in Figure the SEM figure that 2, Fig. 2 is Graphene/metal composite thin film prepared by the embodiment of the present invention 3.As shown in Figure 2, gold grain is evenly distributed at graphenic surface.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 182 Ω/ ~ 200 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 183 Ω/ ~ 199 Ω/.
Embodiment 4:
1. prepare the chlorauric acid solution of 1g/L.
2. the 1g/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and leaves standstill the laminated film making gold particle/graphene film/copper substrate be formed for 3 minutes.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and PET pressing.Form PET/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PET/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PET/ gold particle/graphene film, do with washed with de-ionized water after-blow.
Described Graphene/metal composite thin film is carried out sem observation, the results are shown in Figure the SEM figure that 3, Fig. 3 is Graphene/metal composite thin film prepared by the embodiment of the present invention 4.As shown in Figure 3, gold grain is evenly distributed at graphenic surface.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 170 Ω/ ~ 180 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 175 Ω/ ~ 182 Ω/.
Embodiment 5:
1. prepare the chlorauric acid solution of 0.001mg/L.
2. the 0.001mg/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and standing 24h obtains the laminated film that gold particle/graphene film/copper substrate is formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and PET pressing.Form PET/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PET/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PET/ gold particle/graphene film, do with washed with de-ionized water after-blow.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 220 Ω/ ~ 250 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 223 Ω/ ~ 249 Ω/.
Embodiment 6:
1. prepare the chlorauric acid solution of 0.01mg/L.
2. the 0.01mg/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and leaves standstill the laminated film obtaining gold particle/graphene film/copper substrate for 1 minute and formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. using UV light binding as binding agent, above-mentioned copper/Graphene and PET are crossed roll-in and closes, use the solid machine of UV light to be cured, obtain PET/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PET/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PET/ gold particle/graphene film, do with washed with de-ionized water after-blow.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 198 Ω/ ~ 232 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, placing range is: 201 Ω/ ~ 229 Ω/.
Embodiment 7:
1. prepare the chlorauric acid solution of 0.2mg/L.
2. the 0.2mg/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and standing 10h obtains the laminated film that gold particle/graphene film/copper substrate is formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and PC pressing.Form PC/ gold particle/graphene film/copper underlying structure.
5. above-mentioned PC/ gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of PC/ gold particle/graphene film, do with washed with de-ionized water after-blow.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 208 Ω/ ~ 225 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 211 Ω/ ~ 230 Ω/.
Embodiment 8:
1. prepare the chlorauric acid solution of 0.05g/L.
2. the 0.05g/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and leaves standstill the laminated film obtaining gold particle/graphene film/copper substrate for 10 minutes and formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and quartzy pressing.Form quartz/gold particle/graphene film/copper underlying structure.
5. above-mentioned quartz/gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of quartz/gold particle/graphene film, do with washed with de-ionized water after-blow.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 182 Ω/ ~ 193 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 185 Ω/ ~ 201 Ω/.
Embodiment 9:
1. prepare the chlorauric acid solution of 0.1mg/L.
2. the 0.1mg/L chlorauric acid solution after above-mentioned dilution is put in the copper substrate with graphene film embodiment 1 prepared, and standing 5h obtains the laminated film that gold particle/graphene film/copper substrate is formed.
3. take out above-mentioned laminated film, do with washed with de-ionized water after-blow.
4. by above-mentioned laminated film under 110 DEG C of conditions, hot melt adhesive, as binding agent, crosses roller and quartzy pressing.Form quartz/gold particle/graphene film/copper underlying structure.
5. above-mentioned quartz/gold particle/graphene film/copper underlying structure is put in the ammonium persulfate solution of 10% and etches.
6. after copper is etched completely, obtain the Graphene/metal composite thin film of quartz/gold particle/graphene film, do with washed with de-ionized water after-blow.
7. measure the sheet resistance value of the above-mentioned Graphene/metal composite thin film prepared, sheet resistance scope is: 195 Ω/ ~ 220 Ω/.
8. after above-mentioned Graphene/metal composite thin film being placed 1 month, sheet resistance scope is: 201 Ω/ ~ 225 Ω/.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for Graphene/metal composite thin film, is characterized in that, comprises the following steps:
A) there is the growth substrate of graphene film to immerse in reduced liquid length and carry out reduction reaction, obtain the laminated film of metallics/graphene film/growth substrate;
B) metallics/graphene film in the laminated film of described metallics/graphene film/growth substrate is transferred to target substrate, obtains the Graphene/metal composite thin film of target substrate/metallics/graphene film.
2. preparation method according to claim 1, is characterized in that, described growth substrate is selected from copper substrate or nickel substrate.
3. preparation method according to claim 1, is characterized in that, the water-soluble metal salt in described reduced liquid is one or more in hydrochloro-auric acid, sodium chloraurate, Silver Nitrate, Platinic chloride, sodium platinichloride.
4. preparation method according to claim 1, is characterized in that, in described reduced liquid, the concentration of metal ion is 0.001mg/L ~ 1g/L.
5. preparation method according to claim 1, is characterized in that, described target substrate is selected from PET, PE, PC, PVC, glass, silicon chip or quartz.
6. preparation method according to claim 1, is characterized in that, the time of reduction reaction is 10s ~ 24h.
7. preparation method according to claim 1, is characterized in that, described step B) be specially:
After adopting binding agent the laminated film of described metallics/graphene film/growth substrate and target substrate to be fitted, more described growth substrate is etched, obtain the Graphene/metal composite thin film of target substrate/metallics/graphene film.
8. preparation method according to claim 7, is characterized in that, described binding agent is selected from hot melt adhesive, UV light binding or polyester binding agent.
9. preparation method according to claim 7, is characterized in that, the etching liquid of described etching is selected from ammonium persulphate.
10. Graphene/the metal composite thin film prepared by the preparation method described in claim 1 ~ 9 any one claim, is characterized in that described sheet resistance is 170 ~ 250 Ω/.
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