CN105845195B - A kind of transition metal oxide/graphene composite film and preparation method thereof - Google Patents
A kind of transition metal oxide/graphene composite film and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- -1 transition metal alkoxide Chemical class 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012895 dilution Substances 0.000 claims abstract description 4
- 238000010790 dilution Methods 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 238000004528 spin coating Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- OAWVEVRRALEEIL-UHFFFAOYSA-N propan-2-ol;vanadium Chemical compound [V].CC(C)O OAWVEVRRALEEIL-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- MGRORBOILBLUTP-UHFFFAOYSA-N propan-2-ol tungsten Chemical compound [W].C(C)(C)O MGRORBOILBLUTP-UHFFFAOYSA-N 0.000 claims description 5
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical group CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- AHKFGBCCQCXNJR-UHFFFAOYSA-N molybdenum;propan-2-ol Chemical compound [Mo].CC(C)O AHKFGBCCQCXNJR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UDLNTXAJWMODMV-UHFFFAOYSA-N nickel;propan-2-ol Chemical compound [Ni].CC(C)O UDLNTXAJWMODMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 11
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 238000005485 electric heating Methods 0.000 abstract description 2
- 238000013021 overheating Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 60
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 241000186216 Corynebacterium Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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Abstract
The present invention relates to a kind of transition metal oxide/graphene composite film and preparation method thereof, transition metal alkoxide is doped to it with being spin-coated on graphenic surface after alcohol dissolved dilution, through Overheating Treatment, transition metal oxide/graphene composite film is obtained, the transition metal oxide/graphene composite film includes graphene layer and the transition metal oxide layer being deposited on graphene layer.The present invention is with low cost, easy to operate.After doping treatment, graphenic surface resistance is remarkably decreased, and can keep stable in a long time.Graphene sheet resistance can reduce by 40~50% after doping treatment, and show very excellent stability and light transmission rate.The present invention is to expanding transparent graphene conductive film using significant.Graphene film prepared by the present invention is expected to be used widely in fields such as solar cell, touch-screen, electric heating films.
Description
Technical field
The present invention relates to a kind of preparation method of transition metal oxide/graphene composite film, belong to film material
Expect technical field.
Background technology
Transparent conductive film with good electric conductivity and translucency is widely applied among industrial production.So far it is
Only, material used in transparent conductive film is always ITO, but ITO has a shortcomings, such as ITO acid or alkali environment it
In and it is unstable, near infrared light region transmitance it is not high, lack flexibility and cause it increasingly to go up because of In resource shortages
Price.Graphene has high intensity, chemical stability, good flexibility and electric conductivity so that graphene, which turns into, to be replaced
ITO prepares the excellent material of transparent conductive film.
However, the graphene for being now based on CVD preparation still has substantial amounts of defect, the electric conductivity of graphene result in
Still undesirable, i.e., sheet resistance higher (100-500 Ω/) is the more than ten of transparent conductive film under 85% transmitance
Times, along with the band gap of property zero due to graphene in itself, it is cannot function as semiconductor application.In addition, graphene work function
Than relatively low (4.2~4.6eV) such that it is weaker as the competitiveness of electrode.This is all that graphene extensively should in field of electronic devices
Obstruction.If for example, graphene will as solar cell cathode material, the work function of electrode is preferably left in 5.0eV
The right side, therefore graphene is that will adjust electric conductivity and work function the need for meeting as electrode of solar battery.
Graphene carrier concentration is improved by adulterating, is to improve one of most effectual way of its electrical conductivity.Graphene
Doping is broadly divided into chemical (displacement) doping and adulterated with surface physics.Different from chemical doping, surface physics doping will not be destroyed
The six-membered ring structure of graphene, and only it is the difference by dopant and graphene work function, realize the carrier to graphene
Injection.Thus surface physics doping can significantly improve its carrier number under conditions of carrier mobility is not reduced, and show
Big advantage is shown.The graphenic surface dopant reported at present mainly includes, organic molecule (TFSA, DDQ, F4-
TCNQ etc.), inorganic salts/acid (HNO3, AuCl3, SOCl2Deng), (O such as metal particle and oxidizing gas2, NO2).However,
The doping such as inorganic acid, organic molecule and gas dopant effect is extremely unstable, such as HNO3The Graphene electrodes of doping are in atmosphere
After placing 480 hours, resistance increase by 90%.And metal particle and AuCl3It is too high Deng then cost, it is difficult to large-scale application.
The content of the invention
For the unstable deficiency of resistance after existing graphene doping method cost height, doping, the present invention is intended to provide
A kind of transition metal oxide/graphene composite film and a kind of simple and convenient, inexpensive doped graphene method, can be with bright
It is aobvious to improve graphene conductive and ensure that resistance keeps stable in a long time, so that the bottleneck for solving graphene application is asked
Topic.
In order to solve the above problems, the invention provides a kind of transition metal oxide/graphene composite film, by transition
Metal alkoxide is doped to it with being spin-coated on graphenic surface after alcohol dissolved dilution, through Overheating Treatment, obtains oxo transition metal
Compound/graphene composite film, the transition metal oxide/graphene composite film includes graphene layer and is deposited on graphite
Transition metal oxide layer on alkene layer.
Transition metal alkoxide with after alcohol dissolved dilution, is spin-coated on graphenic surface, eventually passes heat treatment, obtain by the present invention
To transition metal oxide/graphene composite film.The present invention completes transition metal oxide pair in membrane-film preparation process
The doping of graphene, belongs to surface physics doping.After graphenic surface spin coating transition metal oxide, because oxide compares stone
Black alkene work function is high, and the two interface will produce band curvature, so that electronics is injected into metal oxide by graphene, i.e.,
P-type doping occurs for graphene.Different from displacement doping, doping of the transition metal oxide to graphene will not destroy graphene
Six-membered ring structure, thus graphene carrier number can be significantly improved under conditions of carrier mobility is not reduced, and then
The sheet resistance of graphene is significantly reduced, big advantage is shown in terms of the electric conductivity of graphene is improved.Transition metal oxide
Be entrained in the work function for ensureing that graphene is significantly improved in the case of certain light transmission rate, reduce graphene sheet resistance, adulterate stone
Black alkene work function maximum can improve more than 0.3eV, and sheet resistance can at most decline more than 50%.
It is preferred that the composition of the transition metal oxide layer is at least one in metal Mo, V, W and Ni oxide
Plant, preferably metal V oxide.
It is preferred that the transition metal oxide layer thickness is 1nm~20nm, preferably 10nm.
Present invention also offers a kind of preparation method of transition metal oxide/graphene composite film, including：
(1) transition metal alkoxide salting liquid is spun to graphenic surface；
(2) graphene after spin coating obtained by (1) is placed in air atmosphere at 25 DEG C~800 DEG C, preferably 100~500
DEG C, calcine 0.5~24 hour, preferably 1~5 hour, obtain transition metal oxide/graphene composite film.
It is preferred that the transition metal alkoxide is isopropoxide, preferably isopropanol molybdenum, isopropanol tungsten, isopropanol vanadium, different
At least one of propyl alcohol nickel.
It is preferred that the solvent of the transition metal alkoxide salting liquid be ethanol, normal propyl alcohol, isopropanol, glycerine, n-butanol,
At least one of ethylene glycol.
It is preferred that the concentration of the alkoxide solution is more than 0.001mol/L and in below 0.1mol/L, it is preferably
Between 0.001mol/L to 0.016mol/L.
It is preferred that the spin speed of the spin coating is 0 between 5000rpm, preferably 1000 between 5000rpm.
It is preferred that the atmosphere of the calcining is air atmosphere.
The present invention uses metal alkoxide for raw material, uses spin-coating method film forming, is heat-treated in atmosphere, with low cost, operation letter
Just.After doping treatment, graphenic surface resistance is remarkably decreased, and can keep stable in a long time.After doping treatment
Graphene sheet resistance can reduce by 40~50%, and show very excellent stability and light transmission rate.The present invention is to expanding stone
Black alkene transparent conductive film is using significant.Graphene film prepared by the present invention is expected in solar cell, touched
It is used widely in the fields such as screen, electric heating film.
Brief description of the drawings
Fig. 1 is the XRD diffracting spectrums of transition metal oxide/graphene composite film in embodiment 1；
Fig. 2 is the SEM photograph of transition metal oxide/graphene composite film in embodiment 1；
Fig. 3 is the Raman collection of illustrative plates of transition metal oxide/graphene composite film in embodiment 1；
Fig. 4 is that the sheet resistance of transition metal oxide/graphene composite film in embodiment 1 changes over time figure；
Fig. 5 is light transmission of the transition metal oxide/graphene composite film under different calcining heats in embodiment 1
Rate-wavelength curve；
Sheet resistance changes of the Fig. 6 to be heat-treated transition metal oxide/graphene composite film of acquisition under different atmosphere becomes
Gesture figure；
Fig. 7 is that the sheet resistance decline percentage of different material doping gained laminated film in comparative example 1 becomes with heat treatment temperature
Change curve (ordinate negative sign represents that sheet resistance is raised)；
Fig. 8 is that the sheet resistance of gained laminated film in comparative example 2 declines change song of the percentage with isopropanol vanadium solution concentration
Line.
Embodiment
The present invention is further illustrated below in conjunction with drawings and embodiments, it should be appreciated that following embodiments are merely to illustrate
The present invention, is not intended to limit the present invention.
The present invention deposits film forming using the alcoholic solution of transition metal alkoxide as raw material in graphenic surface, in atmosphere at heat
Reason, obtains transition metal oxide/graphene composite film.The present invention completes mixing for transition metal in membrane-film preparation process
Miscellaneous, the composition of wherein transition metal oxide layer is at least one of metal Mo, V, W and Ni oxide, preferably metal V
Oxide.The effect of metal V oxide reduction graphene resistance preferably, can reduce graphene sheet resistance up to more than 50%,
And more than graphene work function 0.3eV can be improved.
The preparation method for transition metal oxide/graphene composite film that the explanation present invention of the example below is provided.
Transition metal alkoxide salting liquid is spun to graphenic surface.Alkoxide of the present invention is in the deposition side of graphenic surface
Method is spin-coating method.Because this method is easily operated and energy consumption is relatively low.
Above-mentioned transition metal alkoxide alkoxide can be but be not limited only to isopropoxide, preferably can for isopropanol molybdenum, isopropanol tungsten,
At least one of isopropanol vanadium, isopropanol nickel.Present invention selection transition metal isopropoxide is because cost is relatively low and is easy to get.
The above-mentioned solvent for being used to dissolve isopropoxide may generally be alcohol, and wherein alcohol includes but is not limited to ethanol, propyl alcohol, isopropyl
At least one of alcohol, glycerine, n-butanol, preferably isopropanol.Because isopropanol it is cheap and with graphene wellability
Well, film-formation result is preferable.
The concentration of above-mentioned transition metal alkoxide salting liquid is more than 0.001mol/L and for below 0.1mol/L, be preferably between
Between 0.001mol/L to 0.016mol/L.Concentration is higher, and film forming is thicker, influences transmitance；Concentration is relatively low, then adulterates effect not
Substantially.
The spin speed of above-mentioned spin coating is between 0 between 5000rpm, being preferably between 1000 between 5000rpm.Spin coating speed
Degree is too high or too low, and film thickness is all undesirable.
Carry out being thermally treated resulting in transition metal oxide/graphene composite film after graphenic surface spin-coating film.
The temperature of above-mentioned heat treatment is preferably between 100 DEG C to 500 DEG C between 25 DEG C to 800 DEG C.Due to
In heat treatment process, sull may proceed to occur chemistry or physical change.Too low temperature, reaction is not yet carried out, and is mixed
Miscellaneous effect promoting is not obvious, or even can decline.Temperature is too high, and may destroy graphene film causes doped graphene electric conductivity
It is deteriorated.In a word, it is heat-treated at a temperature of 25-100 DEG C, compared with undoped with graphene, the resistance of doped graphene film
Substantially reduction is remained to, thus the cost of this method is cheaper.
The atmosphere of heat treatment described above can be air.Because the oxygen in air can improve metal oxide work function,
More multiple carrier is injected among graphene, consolidating doping effect.
The time of heat treatment described above between 0.5 hour to 24 hours, be preferably between 1 hour to 5 hours it
Between.Calcination time is too short to influence the doping level of graphene, and calcination time is long to waste the energy.
The thickness of transition metal oxide layer exists in transition metal oxide/graphene composite film prepared by the present invention
10nm or so (see Fig. 2).The light transmission rate of laminated film is in 85~92% (550nm) left and right (see Fig. 5), and sheet resistance is 100~300
Ω/sq or so (see Fig. 4).
Doped graphene film prepared by the present invention, compared with undoped with graphene film, graphene work function is improved
0.01-2.0eV or so, sheet resistance reduction by 40%~50%.It is positioned in air after 700h, sheet resistance only rises 20%~60%.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
0.01ml isopropanols vanadium (purity 99%, Sigma-Aldrich) is used into 1ml isopropanols, drops in and is transferred to stone
English substrate undoped with graphenic surface, spin coating 1 minute under 5000rpm rotating speeds.Above-mentioned graphene film is placed in tube furnace, with 20
DEG C/min speed be warming up to 300 DEG C, and be incubated 30min, obtain VOxThe transparent graphene conductive film of doping.Accompanying drawing 1 is
Its XRD diffracting spectrum.It can be seen that at such a temperature, VOxIn certain crystallization state, it is in 20.26 ° and 41.26 ° of diffraction maximum pair
Should be in the V of crystalline state2O5(JCPDF#41-1426), crystalline state V is then corresponded in the little diffraction maximum of 24.45 ° of appearance3O7
(JCPDF#27-0940).Film surface SEM photograph is as depicted in figure 2, it can be seen that VOxCrystal grain is in corynebacterium, and length is less than
100nm.Section SEM photograph (accompanying drawing 2b) shows, VOxThe thickness of layer is 10nm or so.The Raman of graphene film before and after doping
Spectrum is as shown in Figure 3, it can be seen that compared with undoped with graphene, and graphene G peaks occur in that by a relatively large margin red after doping
Move, this shows that graphene there occurs that p-type is adulterated.The change of graphene sheet resistance and its stability test result such as accompanying drawing 4 before and after doping
Shown, the sheet resistance of graphene film is 400/sq before doping, and sheet resistance of graphene thin film is 176/sq after doping, and fall reaches
56%.From this figure it can be seen that the stability of sample is very excellent, place in atmosphere after 700h, sheet resistance only rises
59%.Accompanying drawing 5 is undoped with the light transmission rate curve with doped graphene, it is seen that doped graphene is in near-infrared and visible region
With excellent light transmission rate, light transmission rate is about 86% at 550nm.
Embodiment 2
0.01ml isopropanols tungsten (purity 99%, Sigma-Aldrich) is used into 1ml isopropanols, advance transfer is dripped to
To the graphenic surface of quartz substrate, spin coating 1 minute under 5000rpm rotating speeds forms surface covering thin layer WOxGraphene it is thin
Film.Above-mentioned film rises to 300 DEG C with 20 DEG C/min of speed, and is incubated 30min, obtains WOxThe graphene electrically conducting transparent of doping is thin
Film.After measured, the sheet resistance of graphene film is 250/sq after doping, compared with undoped with graphene film (400/sq),
Resistance fall reaches 37.5%.Its light transmission rate at 550nm is 92%.
Comparative example 1
0.01ml isopropanols vanadium and isopropanol tungsten are used into 1ml isopropanols respectively, drips to and is transferred to quartz substrate in advance
Graphenic surface, spin coating 1 minute under 5000rpm rotating speeds forms surface and is covered each by thin layer VOxAnd WOxGraphene film.
Above-mentioned film is placed in tube furnace, in air atmosphere, is warming up to 150 DEG C, 300 DEG C, 400 DEG C with 20 DEG C/min of speed, and protect
Warm 30min, obtains doped graphene transparent conductive film.Sheet resistance of graphene thin film declines percentage as shown in Figure 7 after doping.
As can be seen that the doping effect of isopropanol vanadium is better than isopropanol tungsten.
Comparative example 2
0.0035ml, 0.005ml and 0.015ml isopropanol vanadium 1ml isopropanols are measured respectively, drip to advance transfer
To the graphenic surface of quartz substrate, spin coating 1 minute under 5000rpm rotating speeds forms surface covering VOxThe graphene of thin layer is thin
Film.Above-mentioned graphene film is positioned in tube furnace, is warming up to after certain temperature protects with 20 DEG C/min of speed in atmosphere
Warm 30min, obtains doped graphene transparent conductive film.Sheet resistance of graphene thin film declines percentage as shown in Figure 8 after doping.
As can be seen that after being calcined in air, the more highly doped effect of concentration of isopropanol vanadium is better.
Comparative example 3
0.01ml isopropoxides solution (vanadium and tungsten) is measured respectively and uses 1ml isopropanols, is dripped to and is transferred to quartz in advance
Spin coating 1 minute under the graphenic surface of substrate, 5000rpm rotating speeds, forms surface and is covered each by thin layer VOxAnd WOxGraphene it is thin
Film.Above-mentioned graphene film is positioned in tube furnace, is warming up in atmosphere with 20 DEG C/min of speed after 300 DEG C, is incubated
30min, 1 hour and 3 hours.Obtain the different doped graphene of heat treatment temperature.Test result shows, the resistance of doping film
It is essentially identical with light transmission rate, show that heat treatment time is little to doping influential effect.
Method of testing：Doped graphene film surface sheet resistance is tested using four probe method, Raman spectrometer testing stone is utilized
Black alkene doping level, utilizes ultraviolet-visible-near infrared spectrometer, testing film light transmission rate.
Fig. 6 is to be heat-treated the doped graphene sheet resistance changing trend diagram of acquisition under different atmosphere.As can be known from Fig. 6, adulterate
Graphene film anneal in atmosphere than in argon gas annealing effect it is more notable, doped graphene transparent conductive film electric conductivity
Lifting becomes apparent.
Claims (11)
1. a kind of transition metal oxide/graphene composite film, it is characterised in that by transition metal alkoxide alcohol dissolved dilution
After be spin-coated on graphenic surface it be doped, be heat-treated by being calcined in air atmosphere, obtain transition metal oxide/
Graphene composite film, the transition metal oxide/graphene composite film includes graphene layer and is deposited on graphene layer
On transition metal oxide layer, the transition metal oxide layer composition for metal Mo, V, W and Ni oxide in extremely
Few one kind.
2. transition metal oxide/graphene composite film according to claim 1, it is characterised in that the transition gold
Category oxide layer thicknesses are the nm of 1 nm~20.
3. a kind of preparation method of transition metal oxide/graphene composite film as claimed in claim 1 or 2, its feature exists
In, including：
（1）Transition metal alkoxide salting liquid is spun to graphenic surface；
（2）Will（1）Graphene at 25 DEG C~800 DEG C, is calcined 0.5~24 hour, obtained in air atmosphere after gained spin coating
Cross metal oxide/graphene composite film.
4. preparation method according to claim 3, it is characterised in that will（1）Graphene is in air atmosphere after gained spin coating
In at 100~500 DEG C, calcine 1~5 hour, obtain transition metal oxide/graphene composite film.
5. preparation method according to claim 3, it is characterised in that the transition metal alkoxide is isopropoxide.
6. preparation method according to claim 5, it is characterised in that the isopropoxide be isopropanol molybdenum, isopropanol tungsten,
At least one of isopropanol vanadium, isopropanol nickel.
7. the preparation method according to any one of claim 3-6, it is characterised in that the transition metal alkoxide salting liquid
Solvent is at least one of ethanol, normal propyl alcohol, isopropanol, glycerine, n-butanol, ethylene glycol.
8. preparation method according to claim 3, it is characterised in that the concentration of the alkoxide solution is more than 0.001
Mol/L and in 0.1 below mol/L.
9. preparation method according to claim 8, it is characterised in that the concentration of the alkoxide solution is 0.001 mol/L
To between 0.016 mol/L.
10. preparation method according to claim 3, it is characterised in that the spin speed of the spin coating is 0 to 5000 rpm
Between.
11. preparation method according to claim 10, it is characterised in that the spin speed of the spin coating is 1000 to 5000
Between rpm.
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