CN105239061B - A kind of graphene/metal composite thin film and preparation method thereof - Google Patents
A kind of graphene/metal composite thin film and preparation method thereof Download PDFInfo
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- CN105239061B CN105239061B CN201510624104.4A CN201510624104A CN105239061B CN 105239061 B CN105239061 B CN 105239061B CN 201510624104 A CN201510624104 A CN 201510624104A CN 105239061 B CN105239061 B CN 105239061B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 203
- 239000002905 metal composite material Substances 0.000 title claims abstract description 74
- 239000010409 thin film Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 176
- 239000000758 substrate Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 49
- 229910052802 copper Inorganic materials 0.000 claims description 49
- 229910052737 gold Inorganic materials 0.000 claims description 39
- 239000010931 gold Substances 0.000 claims description 39
- 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 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 239000004831 Hot glue Substances 0.000 claims description 12
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 238000005530 etching Methods 0.000 claims description 5
- 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 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 platinum ion Chemical class 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 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
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 37
- 239000002245 particle Substances 0.000 description 35
- 238000004140 cleaning Methods 0.000 description 11
- 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 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002923 metal particle Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 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
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
The present invention provides a kind of preparation methods of graphene/metal composite thin film, the following steps are included: A) in-situ reducing reaction will be carried out in the growth substrate immersion reducing solution with graphene film, obtain metallic/graphene film/growth substrate laminated film；B metallic/graphene film in the metallic/graphene film/growth substrate laminated film) is transferred to target substrate, obtains target substrate/metallic/graphene film laminated film.Metallic in-situ reducing on graphene film, is saved complex flow and metallic can form good dispersion on graphene film, reduce graphene/metal composite thin film sheet resistance by preparation method provided by the present invention.Metallic is clipped between graphene film and target substrate in the graphene/metal composite thin film being prepared, and is well protected, and the time stability of laminated film sheet resistance is greatly strengthened.
Description
Technical field
The invention belongs to technical field of graphene, and in particular to a kind of graphene/metal composite thin film and preparation method thereof.
Background technique
Graphene be one kind by carbon atom with sp2Hybridized orbit forms the planar material that hexangle type is in honeycomb lattice,
It is the two-dimensional material of single carbon atom thickness, with a thickness of 0.334nm.Graphene is as a kind of its special hole of semi-metallic
Gap structure determines that it has the characteristics that flexibility.Carrier concentration is up to 1013cm inside graphene-2, theoretical mobility energy
Reach 200000cm2/ Vs, and the light transmittance of single-layer graphene reaches 97.7%.These special performances of graphene make it
Wide application prospect is shown in electronic information, energy new material and war industry field.
Especially in transparent conductive film field, graphene has both excellent optics, mechanics and mechanical property and becomes most
Good next-generation transparent conductive film alternative materials.But current graphene strongly limits it there is also the higher problem of impedance
Application in transparent conductive film field.Conventional method is by the method for doping electric conductivity to be further increased, still
Its performance boost is also than relatively limited.And by the compound good electric conductivity that can use metal material of graphene and metal come bridge
The defect of frame graphene film, so that the conductive characteristic of graphene film be substantially improved.
Graphene and metal composite prepare graphene/metal composite thin film at present, need by applying metal Nano structure
Cloth is on graphene or substrate, wherein metal nanoparticle needs in addition synthesis, and process is complicated；Also, metal nano ion
It is easy to happen reunion in coating, to increase graphene/metal composite thin film sheet resistance, and the time stability of sheet resistance
It is poor, therefore finding one kind graphene/metal composite method easy to use is the important of breakthrough graphene film performance bottleneck
Part.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of graphene/metal composite thin film and its system
Preparation Method, preparation method provided by the invention is simple, and the graphene being prepared/metal composite thin film sheet resistance is low, and has
Good time stability.
The present invention provides a kind of preparation methods of graphene/metal composite thin film, comprising the following steps:
A) growth substrate with graphene film is immersed in reducing solution and carries out reduction reaction, obtains metallic/stone
The laminated film of black alkene film/growth substrate；
B) by metallic/graphene film in the metallic/graphene film/growth substrate laminated film
It is transferred to target substrate, obtains target substrate/metallic/graphene film graphene/metal composite thin film.
Preferably, the growth substrate is selected from copper-based bottom or nickel substrate.
Preferably, the water-soluble metal salt in the reducing solution is gold chloride, sodium chloraurate, silver nitrate, chloroplatinic acid, chlorine platinum
One of sour sodium is a variety of.
Preferably, the water-soluble metal salt in the reducing solution is one of gold chloride, chloroplatinic acid or a variety of.
Preferably, the concentration of metal ion is 0.001mg/L~1g/L in the reducing solution.
Preferably, the concentration of metal ion is 0.01mg/L~0.5g/L in the reducing solution.
Preferably, the concentration of metal ion is 0.05mg/L~0.1g/L in the reducing solution
Preferably, the time of reduction reaction is 10s~for 24 hours.
It is preferred that the time of the reduction reaction is 1min~1h.
Preferably, the growth substrate with graphene film is prepared by the following method:
Growth substrate is put into reacting furnace, then reaction gas is passed through into reacting furnace and is reacted, is obtained with graphite
The growth substrate of alkene film；The reaction gas includes hydrogen and gaseous carbon source.
Preferably, the target substrate is selected from PET, PE, PC, PVC, glass, silicon wafer or quartz.
Preferably, the step B) specifically:
The metallic/graphene film/growth substrate laminated film is bonded with target substrate using binder
Afterwards, then by the growth substrate it etches, it is thin to obtain target substrate/metallic/graphene film graphene/metal composite
Film.
Preferably in the binder is selected from hot melt adhesive, UV light binding or polyesters binder.
Preferably, the etching liquid of the etching is selected from ammonium persulfate.
The present invention also provides a kind of graphene/metal composite thin film that above-mentioned preparation method is prepared, sheet resistances 170
~250 Ω/.
Compared with prior art, the present invention provides a kind of preparation method of graphene/metal composite thin film, including it is following
Step: A) by with graphene film growth substrate immerse with metal ion reducing solution in carry out reduction reaction, obtain
To metallic/graphene film/growth substrate laminated film；B) by the metallic/graphene film/growth substrate
Laminated film in metallic/graphene film be transferred to target substrate, obtain target substrate/metallic/graphene
Graphene/metal composite thin film of film.The present invention immerses the growth substrate with graphene film with metal ion
In reducing solution, graphene and growth substrate and the reducing solution with metal ion form primary battery system.Due to described
The metallic element of growing substrate is stronger than the reproducibility of the metallic element of the metal ion in reducing solution, therefore the metal in reducing solution
Ion can be reduced into the metallic of nano-scale, metal salt be reduced into the stabilization formed after metal simple-substance, uniformly, be in
The metal-sol that single dispersity floats on a liquid.Under the mechanism of action of primary battery, metal in the reducing solution from
Son is easily adsorbed on the surface of graphene after in-situ reducing, so as to form graphene/metal composite thin film.This method is saved
Complex flow and metallic can form good dispersion on graphene film, reduces graphene/metal composite
The sheet resistance of film.In the graphene/metal composite thin film being prepared metallic be clipped in graphene film and target substrate it
Between, it is well protected, greatly strengthens the time stability of laminated film sheet resistance.
The result shows that the sheet resistance of graphene/metal composite thin film provided by the invention is 170~250 Ω/, it will be described
Graphene/metal composite thin film is placed a rear resistance in month and is varied less.
Detailed description of the invention
Fig. 1 is graphene/metal composite thin film SEM figure prepared by the embodiment of the present invention 2；
Fig. 2 is graphene/metal composite thin film SEM figure prepared by the embodiment of the present invention 3；
Fig. 3 is graphene/metal composite thin film SEM figure prepared by the embodiment of the present invention 4.
Specific embodiment
The present invention provides a kind of preparation methods of graphene/metal composite thin film, comprising the following steps:
A) growth substrate with graphene film is immersed in reducing solution and carries out reduction reaction, obtains metallic/stone
The laminated film of black alkene film/growth substrate；
B) by metallic/graphene film in the metallic/graphene film/growth substrate laminated film
It is transferred to target substrate, obtains target substrate/metallic/graphene film graphene/metal composite thin film.
The present invention, which first immerses the growth substrate with graphene film in reducing solution, carries out reduction reaction, obtains metal
Particle/graphene film/growth substrate laminated film.
In the present invention, the growth substrate with graphene film is prepared by the following method:
Growth substrate is put into reacting furnace, then reaction gas is passed through into reacting furnace and is reacted, is obtained with graphite
The growth substrate of alkene film；The reaction gas includes hydrogen and gaseous carbon source.
Growth substrate is put into reacting furnace by the present invention, wherein the growth substrate is selected from Cu substrate or Ni substrate, preferably
For Cu substrate.The reacting furnace is preferably chemical vapor deposition stove.
After growth substrate is put into reacting furnace, reaction gas is passed through in Xiang Suoshu reacting furnace and is reacted.In the present invention,
The reaction gas includes hydrogen and gaseous carbon source, wherein the gaseous carbon source is selected from methane and/or ethylene.In reaction gas,
The volume ratio of the hydrogen and the gaseous carbon source is preferably 1~500:0.1~100, more preferably 50~100:10~20.Institute
The temperature for stating reaction is preferably 800~1200 DEG C, more preferably 900~1100 DEG C, most preferably 1000~1090 DEG C.It is described anti-
The time answered is preferably 1min~60min, more preferably 10min~20min.
After reaction, the growth substrate with graphene film is obtained.By the growth base with graphene film
Bottom, which is immersed in reducing solution, carries out reduction reaction, obtains metallic/graphene film/growth substrate laminated film.
In the present invention, the reducing solution is the reducing solution with metal ion, the reducing solution with metal ion
It is configured by the following method:
Water-soluble metal salt is dissolved in deionized water, is uniformly mixed, the reducing solution with metal ion is obtained.
In the present invention, water-soluble metal salt is preferably chlorate or nitrate.More preferably gold chloride, sodium chloraurate,
One of silver nitrate, chloroplatinic acid, platinic sodium chloride are a variety of.More preferably one of gold chloride, chloroplatinic acid or a variety of.It is described
The reproducibility of metal used in growth substrate is better than the reproducibility of metal in the soluble metal compound, the soluble gold
Belonging to metal in compound is preferably one of silver, platinum and gold or a variety of, i.e., the described metal ion is preferably silver ion, platinum ion
With one of gold ion or a variety of.
Preferably, the concentration of metal ion is 0.001mg/L~1g/L in the reducing solution；It is furthermore preferred that the reduction
The concentration of metal ion is 0.01mg/L~0.5g/L in liquid；Most preferably, the concentration of metal ion is in the reducing solution
0.05mg/L~0.1g/L.
The growth substrate with graphene film is immersed in reducing solution and carries out reduction reaction, the present invention is gone back to described
It is compound or roll-to-roll compound can to carry out single sheet there is no specifically limited for the specific method of original reaction.
Wherein, the single sheet is compound carries out by the following method: choosing the growth with graphene film of single sheet
Substrate is soaked in the reducing solution with metal ion, and the metal ion is restored by growth substrate, obtains different shape
Metal nanoparticle or nano wire, graphene film surface crystallization be precipitated, formed metallic/graphene film/growth
The laminated film of substrate.Obtained laminated film is cleaned, drying.The reduction is preferably 10s~for 24 hours, more preferably
For 1min~1h.The present invention is to the method for the cleaning, drying there is no specifically limited, and well known to a person skilled in the art cleanings
The method of drying.In the present invention, the cleaning is preferred rinses or rinses, and it is preferable to use air knife drying or bakings for the drying
Case drying.
The roll-to-roll compound progress by the following method: by the roll-to-roll growth with graphene film for growing and obtaining
Substrate is installed, wherein growth substrate of a part with graphene film is soaked in the solution with metal ion, institute
It states metal ion to be restored by growth substrate, metal nanoparticle or nano wire of different shapes is obtained, on graphene film surface
Crystallization is precipitated, and forms metallic/graphene film/growth substrate laminated film, later, roll-to-roll set composite starting,
The air knife placed before winding end, for the remaining solution of film surface is blown off, by obtained metallic/graphene film/
The laminated film of growth substrate is wound, and the growth substrate uncoiling with graphene film continues above-mentioned reduction reaction, until obtaining
The metallic of entire volume/graphene film/growth substrate laminated film.The speed of service of the roll-to-roll set composite is preferred
For 0.01m/min~5m/min, more preferably 0.1m/min~1m/min.The reduction is preferably 10s~for 24 hours, more preferably
For 1min~1h.
It is after obtaining metallic/graphene film/growth substrate laminated film, the metallic/graphene is thin
Metallic/graphene film in film/growth substrate laminated film is transferred to target substrate, obtains target substrate/metal
Particle/graphene film graphene/metal composite thin film.
The present invention there is no specifically limited, preferably shifts the method for the transfer by the following method:
The metallic/graphene film/growth substrate laminated film is bonded with target substrate using binder
Afterwards, then by the growth substrate it etches, it is thin to obtain target substrate/metallic/graphene film graphene/metal composite
Film.
Firstly, using binder by metallic/graphene film/growth substrate laminated film and target substrate
Fitting, in the present invention, the binder be selected from hot melt adhesive, UV light binding or polyesters binder, more preferably hot melt adhesive or
UV light binding.The target substrate is selected from PET, PE, PC, PVC, glass, silicon wafer or quartz, more preferably PET.
Then, the growth substrate is etched, present invention preferably employs ammonium persulfate solutions as etching liquid, the over cure
The concentration of acid ammonium solution is preferably 5wt%~20wt%, and in certain specific embodiments of the invention, the ammonium persulfate is molten
The concentration of liquid is 10wt%.
After growth substrate is etched, graphene/metal composite thin film is obtained, the graphene/metal composite thin film is mesh
Mark substrate/metallic/graphene film three-layer composite structure.
Wherein, metallic/graphene film/growth substrate laminated film of the entire volume is in roll-to-roll transfer device
It is middle completion with target substrate be bonded and the etch step of growth substrate, obtain graphene/metal composite thin film of entire volume.
The present invention also provides a kind of graphene/metal composite thin films that above-mentioned preparation method is prepared.
The preparation method of graphene/metal composite thin film provided by the present invention is by metal ion in-situ reducing in graphene
On film, saves complex flow and metallic is uniformly dispersed on graphene film, reduce graphene/metal composite
The sheet resistance of film.In the graphene/metal composite thin film being prepared metallic be clipped in graphene film and target substrate it
Between, it is well protected, greatly strengthens the time stability of laminated film sheet resistance.The result shows that provided by the invention
Graphene/metal composite thin film sheet resistance is 170~250 Ω/, and the graphene/metal composite thin film is placed one month
Rear resistance varies less.
For a further understanding of the present invention, below with reference to embodiment to graphene/metal composite thin film provided by the invention
And preparation method thereof be illustrated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Copper-based bottom is put into chemical gas phase reaction furnace, is then passed through hydrogen and methane into the chemical gas phase reaction furnace
Gas is reacted under conditions of 1000 DEG C, obtains the copper-based bottom with graphene film, wherein the hydrogen and methane
The volume ratio of gas is 10:1.
Comparative example 1
1. the copper-based bottom with graphene film prepared by embodiment 1, under the conditions of 110 DEG C, hot melt adhesive is as bonding
Agent, crosses roller and PET is pressed.Form copper/graphene/PET construction.
2. above-mentioned copper/graphene/PET construction to be put in the ammonium persulfate solution of 10wt% and etch.
3. obtaining the laminated film of PET/ graphene after copper is etched completely, dried up after being cleaned with deionized water.
4. measuring the sheet resistance value of above-mentioned laminated film, sheet resistance range are as follows: 300 Ω/~350 Ω/.
Embodiment 2
1. preparing the chlorauric acid solution of 0.5g/L.
2. it is molten that the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.5g/L gold chloride after above-mentioned dilution
In liquid, stands and obtain within 1 minute the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and PET is pressed as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form PET/
Gold particle/graphene film/copper-based bottom structure.
5. above-mentioned PET/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PET/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
Graphene/the metal composite thin film is scanned electron microscope observation, the result is shown in Figure 1, Fig. 1 is the present invention
Graphene/metal composite thin film SEM figure prepared by embodiment 2.As shown in Figure 1, gold particle is evenly distributed on the surface of graphene.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 185 Ω/~
210Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 190 Ω/~220 Ω/.
Embodiment 3:
1. preparing the chlorauric acid solution of 0.1g/L.
2. it is molten that the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.1g/L gold chloride after above-mentioned dilution
In liquid, stands and obtain within 10 minutes the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and PET is pressed as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form PET/
Gold particle/graphene film/copper-based bottom structure.
5. above-mentioned PET/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PET/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
Graphene/the metal composite thin film is scanned electron microscope observation, as a result sees that Fig. 2, Fig. 2 are the present invention
Graphene/metal composite thin film SEM figure prepared by embodiment 3.As shown in Fig. 2, gold particle is evenly distributed on the surface of graphene.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 182 Ω/~
200Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 183 Ω/~199 Ω/.
Embodiment 4:
1. preparing the chlorauric acid solution of 1g/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 1g/L chlorauric acid solution after above-mentioned dilution
In, stand the laminated film for forming gold particle/graphene film/copper-based bottom.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and PET is pressed as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form PET/
Gold particle/graphene film/copper-based bottom structure.
5. above-mentioned PET/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PET/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
Graphene/the metal composite thin film is scanned electron microscope observation, as a result sees that Fig. 3, Fig. 3 are the present invention
Graphene/metal composite thin film SEM figure prepared by embodiment 4.As shown in Fig. 3, gold particle is distributed on the surface of graphene
It is even.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 170 Ω/~
180Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 175 Ω/~182 Ω/.
Embodiment 5:
1. preparing the chlorauric acid solution of 0.001mg/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.001mg/L chlorine gold after above-mentioned dilution
In acid solution, stands and obtain the laminated film that gold particle/graphene film/copper-based bottom is formed for 24 hours.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and PET is pressed as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form PET/
Gold particle/graphene film/copper-based bottom structure.
5. above-mentioned PET/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PET/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 220 Ω/~
250Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 223 Ω/~249 Ω/.
Embodiment 6:
1. preparing the chlorauric acid solution of 0.01mg/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.01mg/L gold chloride after above-mentioned dilution
In solution, stands and obtain within 1 minute the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. above-mentioned copper/graphene and PET are crossed roll press using UV light binding as binder, consolidates machine using UV light and carry out
Solidification, obtains PET/ gold particle/graphene film/copper-based bottom structure.
5. above-mentioned PET/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PET/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 198 Ω/~
232Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, placing range are as follows: 201 Ω/~229 Ω/.
Embodiment 7:
1. preparing the chlorauric acid solution of 0.2mg/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.2mg/L gold chloride after above-mentioned dilution
In solution, stands 10h and obtain the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and PC is pressed as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form PC/ gold
Particle/graphene film/copper-based bottom structure.
5. above-mentioned PC/ gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and etch.
6. obtaining PC/ gold particle/graphene film graphene/metal composite thin film after copper is etched completely, spending
It is dried up after ionized water cleaning.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 208 Ω/~
225Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 211 Ω/~230 Ω/.
Embodiment 8:
1. preparing the chlorauric acid solution of 0.05g/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.05g/L gold chloride after above-mentioned dilution
In solution, stands and obtain within 10 minutes the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and quartz presses as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form stone
English/gold particle/graphene film/copper-based bottom structure.
5. above-mentioned quartz/gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and carve
Erosion.
6. obtaining quartz/gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 182 Ω/~
193Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 185 Ω/~201 Ω/.
Embodiment 9:
1. preparing the chlorauric acid solution of 0.1mg/L.
2. the copper-based bottom with graphene film prepared by embodiment 1 is put into the 0.1mg/L gold chloride after above-mentioned dilution
In solution, stands 5h and obtain the laminated film that gold particle/graphene film/copper-based bottom is formed.
3. taking out above-mentioned laminated film, dried up after being cleaned with deionized water.
4. hot melt adhesive crosses roller and quartz presses as binder by above-mentioned laminated film under the conditions of 110 DEG C.Form stone
English/gold particle/graphene film/copper-based bottom structure.
5. above-mentioned quartz/gold particle/graphene film/copper-based bottom structure to be put in 10% ammonium persulfate solution and carve
Erosion.
6. obtaining quartz/gold particle/graphene film graphene/metal composite thin film after copper is etched completely, use
It is dried up after deionized water cleaning.
7. measuring the above-mentioned graphene/metal composite thin film sheet resistance value being prepared, sheet resistance range are as follows: 195 Ω/~
220Ω/□。
8. after above-mentioned graphene/metal composite thin film is placed 1 month, sheet resistance range are as follows: 201 Ω/~225 Ω/.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of graphene/metal composite thin film, which comprises the following steps:
A) growth substrate with graphene film is immersed in reducing solution and carries out reduction reaction, obtains metallic/graphene
Film/growth substrate laminated film；The reducing solution be the reducing solution with metal ion, the metal ion be silver from
One of son, platinum ion and gold ion are a variety of, and the concentration of metal ion is 1g/L in the reducing solution；
The growth substrate with graphene film is prepared by the following method:
Growth substrate is put into reacting furnace, then reaction gas is passed through into reacting furnace and is reacted, is obtained thin with graphene
The growth substrate of film；The reaction gas includes hydrogen and gaseous carbon source；
The growth substrate is selected from Cu substrate or Ni substrate；
The reacting furnace is chemical vapor deposition stove；
The volume ratio of the hydrogen and the gaseous carbon source is 1~500:0.1~100；
The temperature of the reaction is 800~1200 DEG C；
The time of the reaction is 1min~60min；
B) metallic in the metallic/graphene film/growth substrate laminated film/graphene film is shifted
To target substrate, target substrate/metallic/graphene film graphene/metal composite thin film is obtained.
2. preparation method according to claim 1, which is characterized in that the growth substrate is selected from copper-based bottom or nickel substrate.
3. preparation method according to claim 1, which is characterized in that the reducing solution with metal ion is according to following
Method is configured:
Water-soluble metal salt is dissolved in deionized water, is uniformly mixed, the reducing solution with metal ion is obtained；The reduction
Water-soluble metal salt in liquid is one of gold chloride, sodium chloraurate, silver nitrate, chloroplatinic acid, platinic sodium chloride or a variety of.
4. preparation method according to claim 1, which is characterized in that the target substrate is selected from PET, PE, PC, PVC, glass
Glass, silicon wafer or quartz.
5. preparation method according to claim 1, which is characterized in that the time of reduction reaction is 10s~for 24 hours.
6. preparation method according to claim 1, which is characterized in that the step B) specifically:
After the metallic/graphene film/growth substrate laminated film is bonded with target substrate using binder, then
The growth substrate is etched, target substrate/metallic/graphene film graphene/metal composite thin film is obtained.
7. preparation method according to claim 6, which is characterized in that the binder be selected from hot melt adhesive, UV light binding or
Polyesters binder.
8. preparation method according to claim 6, which is characterized in that the etching liquid of the etching is selected from ammonium persulfate.
9. a kind of graphene/metal that the preparation method as described in claim 1~8 any one claim is prepared is multiple
Close film, which is characterized in that the sheet resistance of the graphene/metal composite thin film is 170~180 Ω/.
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