CN105845195A - Transition metallic oxide/ graphene composite film and preparing method thereof - Google Patents
Transition metallic oxide/ graphene composite film and preparing method thereof Download PDFInfo
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- CN105845195A CN105845195A CN201610182599.4A CN201610182599A CN105845195A CN 105845195 A CN105845195 A CN 105845195A CN 201610182599 A CN201610182599 A CN 201610182599A CN 105845195 A CN105845195 A CN 105845195A
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- H—ELECTRICITY
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- 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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- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater 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—Heater 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
Abstract
The invention relates to a transition metallic oxide/ graphene composite film and a preparing method thereof. The preparing method includes the steps of dissolving and diluting alcohol for transitional metal alkoxides, spin coating the dissolved and diluted alcohol on the surface of graphene to dope the graphene, and obtaining the transition metallic oxide/ graphene composite film after thermal treatment, wherein the transition metallic oxide/ graphene composite film comprises a graphene layer and a transition metallic oxide deposited on the graphene layer. The low is cost, and operation is easy. After doping processing, the surface resistance of graphene is substantially reduced and remains stable for a long time. After doping processing, the square resistance of the graphene is reduced by 40-50 %, and the high stability and high light transmissivity are ensured, The transition metallic oxide/ graphene composite film and preparing method thereof are of great importance for expanding the application of the transition metallic oxide/ graphene composite film. The transition metallic oxide/ graphene composite film can be applicable to solar cell, touch screens, electric heating films and other fields.
Description
Technical field
The present invention relates to the preparation method of a kind of transition metal oxide/graphene composite film, belong to thin-film material skill
Art field.
Background technology
The transparent conductive film with good electric conductivity and light transmission is widely applied among commercial production.Up to now,
The material that transparent conductive film is used is always ITO, but ITO has shortcomings, such as ITO acid or alkali environment it
In and unstable, near infrared light region, transmitance is the highest, lack flexibility and cause it day by day to go up because of In resource shortage
Price.Graphene has high intensity, chemical stability, good flexibility and electric conductivity so that Graphene becomes replacement
ITO prepares the excellent material of transparent conductive film.
But, it is now based on Graphene prepared by CVD and still there is substantial amounts of defect, result in the electric conductivity of Graphene
The most undesirable, i.e. sheet resistance higher (100-500 Ω/) is under the transmitance of 85%, is the tens of transparent conductive film
Times, add character zero band gap due to Graphene itself so that it is cannot function as quasiconductor application.It addition, Graphene work function
Make it more weak as the competitiveness of electrode than relatively low (4.2～4.6eV).This is all that Graphene extensively should in field of electronic devices
Obstruction.Such as, if Graphene will be as the cathode material of solaode, the work function of electrode is preferably left at 5.0eV
The right side, therefore Graphene is to meet the needs as electrode of solar battery to regulate electric conductivity and work function.
Improve Graphene carrier concentration by doping, be one of most effectual way improving its electrical conductivity.Mixing of Graphene
The miscellaneous chemistry (displacement) that is broadly divided into adulterates and surface physics doping.Different from chemical doping, surface physics doping will not destroy stone
The six-membered ring structure of ink alkene, and only it is made by the difference of adulterant and Graphene work function, it is achieved the carrier of Graphene is noted
Enter.Thus surface physics doping can significantly improve its carrier number under conditions of not reducing carrier mobility, demonstrate
Big advantage.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).But, the doping effect extremely unstable such as mineral acid, organic molecule and gas dopant, such as HNO3The graphite of doping
After alkene electrode places 480 hours in atmosphere, resistance increases by 90%.And metal particle and AuCl3Deng then high cost, it is difficult to
Large-scale application.
Summary of the invention
For the deficiency that resistance after existing Graphene doping method cost height, doping is unstable, it is desirable to provide one
Plant transition metal oxide/graphene composite film and a kind of simple and convenient, method of low cost doped graphene, can be obvious
Improve graphene conductive and ensure that resistance keeps stable in a long time, thus solving the bottleneck problem of Graphene application.
In order to solve the problems referred to above, the invention provides a kind of transition metal oxide/graphene composite film, by transition gold
It is spin-coated on graphenic surface after belonging to alkoxide alcohol dissolved dilution it is doped, through Overheating Treatment, obtains transition metal oxide
/ graphene composite film, described transition metal oxide/graphene composite film includes graphene layer and is deposited on graphene layer
Transition metal oxide layer.
Transition metal alkoxide with after alcohol dissolved dilution, is spin-coated on graphenic surface, eventually passes heat treatment by the present invention,
To transition metal oxide/graphene composite film.The present invention completes transition metal oxide to stone in membrane-film preparation process
The doping of ink alkene, belongs to surface physics doping.When after graphenic surface spin coating transition metal oxide, owing to oxide compares graphite
Alkene work function is high, and the two interface will produce band curvature, so that electronics is injected in metal-oxide by Graphene, i.e. and stone
Ink alkene generation p-type doping.Different from displacement doping, the doping of Graphene will not be destroyed the six of Graphene by transition metal oxide
Ring structure, thus Graphene carrier number can be significantly improved under conditions of not reducing carrier mobility, and then significantly
Reduce the sheet resistance of Graphene, in terms of improving the electric conductivity of Graphene, demonstrate big advantage.The doping of transition metal oxide
In the case of ensureing certain light transmission rate, significantly improve the work function of Graphene, reduce Graphene sheet resistance, doped graphene work content
Number maximum can improve more than 0.3eV, and sheet resistance at most can decline more than 50%.
It is preferred that in the oxide consisting of metal Mo, V, W and Ni of described transition metal oxide layer at least
One, the preferably oxide of metal V.
It is preferred that described transition metal oxide layer thickness is 1nm～20nm, preferably 10nm.
Present invention also offers the preparation method of a kind of transition metal oxide/graphene composite film, including:
(1) transition metal alkoxide saline solution is spun to graphenic surface；
(2) Graphene after (1) gained spin coating is placed in air atmosphere at 25 DEG C～800 DEG C, preferably 100～500 DEG C, forges
Burn 0.5～24 hour, preferably 1～5 hour, obtain transition metal oxide/graphene composite film.
It is preferred that described transition metal alkoxide is isopropoxide, preferably isopropanol molybdenum, isopropanol tungsten, isopropanol vanadium, different
At least one in propanol nickel.
It is preferred that the solvent of described transition metal alkoxide saline solution is ethanol, normal propyl alcohol, isopropanol, glycerol, positive fourth
At least one in alcohol, ethylene glycol.
It is preferred that the concentration of described alkoxide solution is more than 0.001mol/L and at below 0.1mol/L, preferably 0.001
Between mol/L to 0.016mol/L.
It is preferred that the spin speed of described spin coating is between 0 to 5000rpm, preferably 1000 to 5000rpm it
Between.
It is preferred that the atmosphere of described calcining is air atmosphere.
The present invention uses metal alkoxide to be raw material, uses spin-coating method film forming, in atmosphere heat treatment, 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 shows the most excellent stability and light transmission rate.The present invention is to expanding graphite
The application of alkene transparent conductive film is significant.Graphene film prepared by the present invention be expected solaode, touch screen,
It is used widely in the fields such as electric heating film.
Accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum 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 in embodiment 1, the sheet resistance of transition metal oxide/graphene composite film changes over figure；
Fig. 5 is that in embodiment 1, transition metal oxide/graphene composite film light transmission rate-wavelength under different calcining heats is bent
Line；
Fig. 6 is the sheet resistance changing trend diagram of transition metal oxide/graphene composite film that heat treatment obtains under different atmosphere；
Fig. 7 is that the sheet resistance decline percentage ratio of different material doping gained laminated film in comparative example 1 is (vertical with heat treatment cycle curve
Coordinate negative sign represents that sheet resistance raises)；
Fig. 8 is that the sheet resistance of gained laminated film in comparative example 2 declines the percentage ratio change curve with isopropanol vanadium solution concentration.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that following embodiment is merely to illustrate this below in conjunction with drawings and embodiments
Invention, and the unrestricted present invention.
The present invention, with the alcoholic solution of transition metal alkoxide as raw material, deposits film forming at graphenic surface, in atmosphere at heat
Reason, obtains transition metal oxide/graphene composite film.The present invention completes mixing of transition metal in membrane-film preparation process
Miscellaneous, wherein at least one in the oxide consisting of metal Mo, V, W and Ni of transition metal oxide layer, it is preferably
The oxide of metal V.The effect that the oxide of metal V reduces Graphene resistance is best, it is possible to reduces Graphene sheet resistance and reaches
More than 50%, and more than Graphene work function 0.3eV can be improved.
The preparation method of transition metal oxide/graphene composite film that the explanation present invention of the example below provides.
Transition metal alkoxide saline solution is spun to graphenic surface.Alkoxide of the present invention is at the deposition process of graphenic surface
For spin-coating method.Because the 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, can be preferably isopropanol molybdenum, isopropanol tungsten,
At least one in isopropanol vanadium, isopropanol nickel.The present invention selects transition metal isopropoxide because cost is relatively low and is easy to get.
The above-mentioned solvent for dissolving isopropoxide may generally be alcohol, and wherein alcohol includes but not limited to ethanol, propanol, isopropyl
At least one in alcohol, glycerol, n-butyl alcohol, preferably isopropanol.Because isopropanol is cheap and infiltrates with Graphene
Property good, film-formation result is preferable.
The concentration of above-mentioned transition metal alkoxide saline solution more than 0.001mol/L and be below 0.1mol/L, preferably between
Between 0.001mol/L to 0.016mol/L.Concentration is higher, and film forming is thicker, affects transmitance；Concentration is relatively low, then effect of adulterating
The most inconspicuous.
The spin speed of above-mentioned spin coating, between 0 to 5000rpm, is preferably between 1000 to 5000rpm.Spin coating
Speed is too high or too low, and film thickness is the most 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, between 25 DEG C to 800 DEG C, is preferably between 100 DEG C to 500 DEG C.Due to
In heat treatment process, sull may proceed to chemistry or physical change.Too low temperature, reaction is not yet carried out, and mixes
Miscellaneous effect promoting is inconspicuous, even can decline.Temperature is too high, may destroy graphene film and cause doped graphene electric conductivity
It is deteriorated.In a word, though heat treatment at a temperature of 25-100 DEG C, compared with undoped p Graphene, the resistance of doped graphene thin film
Remain to substantially reduce, 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, note
Enter more multiple carrier among Graphene, consolidate doping effect.
The time of heat treatment described above between 0.5 hour to 24 hour, be preferably between 1 hour to 5 hour it
Between.The too short doping level that can affect Graphene of calcination time, calcination time is long can waste the energy.
In transition metal oxide/graphene composite film prepared by the present invention, the thickness of transition metal oxide layer is at 10nm
Left and right (see Fig. 2).The light transmission rate of laminated film 85～92% (550nm) left and right (see Fig. 5), sheet resistance be 100～
300 Ω/about sq (see Fig. 4).
Doped graphene thin film prepared by the present invention, compared with undoped p graphene film, Graphene work function improves 0.01-
About 2.0eV, sheet resistance reduces by 40%～50%.Being positioned in air after 700h, sheet resistance only rises 20%～60%.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
0.01ml isopropanol vanadium (purity 99%, Sigma-Aldrich) is used 1ml isopropanol, drops in and be transferred to quartz substrate not
Doped graphene surface, spin coating 1 minute under 5000rpm rotating speed.Above-mentioned graphene film is placed in tube furnace, with 20 DEG C/min
Ramp to 300 DEG C, and be incubated 30min, obtain VOxThe transparent graphene conductive film of doping.Accompanying drawing 1 is it
XRD diffracting spectrum.Can be seen that at such a temperature, VOxIn certain crystallization state, it is at 20.26 ° and the diffraction of 41.26 °
Peak is corresponding to the V of crystalline state2O5(JCPDF#41-1426), 24.45 ° of little diffraction maximums occurred then corresponding to crystalline state
V3O7(JCPDF#27-0940).Film surface SEM photograph is as depicted in figure 2, it can be seen that VOxCrystal grain is corynebacterium,
Length is less than 100nm.Cross section SEM photograph (accompanying drawing 2b) shows, VOxThe thickness of layer is about 10nm.Stone before and after doping
The Raman spectrum of ink alkene thin film is as shown in Figure 3, it can be seen that compared with undoped p Graphene, after doping, Graphene G peak goes out
Having showed red shift by a relatively large margin, this shows that Graphene there occurs that p-type is adulterated.The change of Graphene sheet resistance and stability thereof before and after doping
As shown in Figure 4, before doping, the sheet resistance of graphene film is 400/sq to test result, and after doping, sheet resistance of graphene thin film is
176/sq, fall reaches 56%.From this figure it can be seen that the stability of sample is the most excellent, place in atmosphere
After 700h, sheet resistance only rises 59%.Accompanying drawing 5 is the light transmission rate curve of undoped p and doped graphene, it is seen that doping stone
Ink alkene has the light transmission rate of excellence at near-infrared and visible region, and at 550nm, light transmission rate is about 86%.
Embodiment 2
0.01ml isopropanol tungsten (purity 99%, Sigma-Aldrich) is used 1ml isopropanol, drips to be transferred to quartz base in advance
The graphenic surface at the end, spin coating 1 minute under 5000rpm rotating speed, form surface and cover thin layer WOxGraphene film.On
State thin film and rise to 300 DEG C with 20 DEG C/min of speed, and be incubated 30min, it is thus achieved that WOxThe Graphene electrically conducting transparent of doping is thin
Film.After measured, after doping, the sheet resistance of graphene film is 250/sq, with undoped p graphene film (400/sq) phase
Ratio, resistance fall reaches 37.5%.Its light transmission rate at 550nm is 92%.
Comparative example 1
0.01ml isopropanol vanadium and isopropanol tungsten are used 1ml isopropanol respectively, drips to be transferred in advance the Graphene of quartz substrate
Surface, spin coating 1 minute under 5000rpm rotating speed, form surface and be covered each by thin layer VOxAnd WOxGraphene film.On
State thin film to be placed in tube furnace, in air atmosphere, with 20 DEG C/min of ramp to 150 DEG C, 300 DEG C, 400 DEG C, and
Insulation 30min, it is thus achieved that doped graphene transparent conductive film.After doping, sheet resistance of graphene thin film declines percentage such as accompanying drawing 7 institute
Show.It can be seen that the doping effect of isopropanol vanadium is better than isopropanol tungsten.
Comparative example 2
Measure 0.0035ml, 0.005ml and 0.015ml isopropanol vanadium 1ml isopropanol respectively, drip to be transferred in advance quartz
The graphenic surface of substrate, spin coating 1 minute under 5000rpm rotating speed, form surface and cover VOxThe graphene film of thin layer.Will
Above-mentioned graphene film is positioned in tube furnace, is incubated in atmosphere after 20 DEG C/min of ramp to uniform temperature
30min, obtains doped graphene transparent conductive film.After doping, sheet resistance of graphene thin film declines percentage ratio as shown in Figure 8.
It can be seen that in air after calcining, the most highly doped effect of concentration of isopropanol vanadium is the best.
Comparative example 3
Measure 0.01ml isopropoxide solution (vanadium and tungsten) respectively and use 1ml isopropanol, drip to be transferred in advance quartz substrate
Graphenic surface, spin coating 1 minute under 5000rpm rotating speed, form surface and be covered each by thin layer VOxAnd WOxGraphene thin
Film.Above-mentioned graphene film is positioned in tube furnace, in atmosphere with 20 DEG C/min of ramp to after 300 DEG C, protects
Temperature 30min, 1 hour and 3 hours.Obtain the doped graphene that heat treatment temperature is different.Test result shows, doping film
Resistance and light transmission rate essentially identical, show heat treatment time to doping influential effect little.
Method of testing: utilize four probe method to test doped graphene film surface sheet resistance, utilizes Raman spectrometer to test graphite
Alkene doping level, utilizes ultraviolet-visible-near infrared spectrometer, testing film light transmission rate.
Fig. 6 is the doped graphene sheet resistance changing trend diagram that under different atmosphere, heat treatment obtains.As can be known from Fig. 6, doping
Graphene film is annealed more notable than annealing effect in argon in atmosphere, and doped graphene transparent conductive film electric conductivity carries
Rise and become apparent from.
Claims (9)
1. transition metal oxide/graphene composite film, it is characterized in that, by being spin-coated on graphenic surface after transition metal alkoxide alcohol dissolved dilution, it is doped, through Overheating Treatment, obtaining transition metal oxide/graphene composite film, described transition metal oxide/graphene composite film includes graphene layer and the transition metal oxide layer being deposited on graphene layer.
Transition metal oxide/graphene composite film the most according to claim 1, it is characterised in that at least one in the oxide consisting of metal Mo, V, W and Ni of described transition metal oxide layer.
Transition metal oxide/graphene composite film the most according to claim 1 and 2, it is characterised in that described transition metal oxide layer thickness is 1 nm～20 nm.
4. the preparation method of transition metal oxide/graphene composite film as according to any one of claim 1-3, it is characterised in that including:
(1) transition metal alkoxide saline solution is spun to graphenic surface；
(2) by Graphene after (1) gained spin coating 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.
At least one in preparation method the most according to claim 4, it is characterised in that described transition metal alkoxide is isopropoxide, preferably isopropanol molybdenum, isopropanol tungsten, isopropanol vanadium, isopropanol nickel.
6. according to the preparation method described in claim 4 or 5, it is characterised in that the solvent of described transition metal alkoxide saline solution is at least one in ethanol, normal propyl alcohol, isopropanol, glycerol, n-butyl alcohol, ethylene glycol.
7. according to the preparation method according to any one of claim 4-6, it is characterised in that the concentration of described alkoxide solution is more than 0.001
Mol/L and at 0.1 below mol/L, between preferably 0.001 mol/L to 0.016 mol/L.
8. according to the preparation method according to any one of claim 4-7, it is characterised in that the spin speed of described spin coating is between 0 to 5000 rpm, between preferably 1000 to 5000 rpm.
9. according to the preparation method according to any one of claim 4-8, it is characterised in that the atmosphere of described calcining is air atmosphere.
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Cited By (4)
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| CN107123468A (en) * | 2017-04-27 | 2017-09-01 | 浙江大学 | A kind of transparent conductive film containing function point analysis layer |
| CN107567117A (en) * | 2017-07-19 | 2018-01-09 | 无锡舒玛天科新能源技术有限公司 | A kind of transparent flexible glass film heater of high-efficiency soft and preparation method thereof |
| CN109694057A (en) * | 2017-10-24 | 2019-04-30 | 中国海洋大学 | A kind of preparation method of Flexible graphene heating film |
| CN110391052A (en) * | 2019-06-27 | 2019-10-29 | 惠科股份有限公司 | A kind of flexible compound conductive film and preparation method thereof and display panel |
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| CN110391052A (en) * | 2019-06-27 | 2019-10-29 | 惠科股份有限公司 | A kind of flexible compound conductive film and preparation method thereof and display panel |
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