CN107403658B - A kind of high conductivity graphene film and preparation method thereof - Google Patents
A kind of high conductivity graphene film and preparation method thereof Download PDFInfo
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- CN107403658B CN107403658B CN201710579772.9A CN201710579772A CN107403658B CN 107403658 B CN107403658 B CN 107403658B CN 201710579772 A CN201710579772 A CN 201710579772A CN 107403658 B CN107403658 B CN 107403658B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention discloses a kind of high conductivity graphene films and preparation method thereof.The preparation method includes the following steps: the airflow direction along carrier gas, graphene film/copper foil structure of composite membrane and polyacrylonitrile fibre membrane/copper foil structure of composite membrane are sequentially placed into quartz chamber body, it is passed through carrier gas and heats up, carry out gas phase reaction under vacuum conditions to get high conductivity graphene film is arrived；Graphene film/copper foil structure of composite membrane is the composite construction of copper foil with the graphene film being coated on copper foil surface；Polyacrylonitrile fibre membrane/copper foil composite membrane is the composite construction of copper foil with the polyacrylonitrile fibre membrane being coated on copper foil surface.Present invention process is simple and easy, and involved electrostatic spinning, low pressure chemical vapor deposition are all mature technologies.Gas-phase chemical reaction is very efficient and uniform to the functionalization of graphene film.The electric conductivity for the functionalization graphene film that the present invention obtains improves 40% or more, highly significant, and influences on the translucency of graphene film very small.
Description
Technical field
The present invention relates to a kind of high conductivity graphene films and preparation method thereof.
Background technique
Graphene is by single layer of carbon atom with sp2The two-dimensional material that hydridization is formed, it has stable physicochemical properties,
Excellent mechanical strength, fabulous electrical and thermal conductivity performance are all widely used in numerous areas, especially can be used as flexible and transparent
Conductive film is applied to next-generation flexible electronic device, flexible touch screen etc..Compared to traditional transparent conductive film (ITO,
AZO, conducting polymer etc.), the electric conductivity of graphene film is less than normal.Therefore, development improves the steady of graphene film electric conductivity
The method of determining is very necessary.The method for improving graphene film electric conductivity at present includes the following categories: 1, graphene lattice
Atom replace, as nitrogen is mixed.This method can reduce mobility while increasing the carrier concentration in graphene film, by
It is destroyed in the perfect lattice of graphene.2, graphene film adsorbed chemical species, such as MoOxFilm, Au nano particle and
Other organic molecules.This method is unstable, is easy failure.3, the chemistry functional of graphene film such as utilizes organic chemistry
Reaction.This method often relates to complicated chemical reaction, it is difficult to control.
Therefore, development improves the high-efficient simple method of graphene film electric conductivity, for promoting graphene film in flexibility
Practical application in device is extremely important.
Summary of the invention
The object of the present invention is to provide a kind of high conductivity graphene film and preparation method thereof, the present invention passes through step letter
Single gas-phase chemical reaction, can directly carry out on CVD graphene/copper foil of initial growth.
The preparation method of high conductivity graphene film provided by the present invention, includes the following steps:
It is along the airflow direction of carrier gas, graphene film/copper foil structure of composite membrane and polyacrylonitrile fibre membrane/copper foil is compound
Membrane structure is sequentially placed into quartz chamber body, is passed through the carrier gas and is heated up, and carries out gas phase reaction under vacuum conditions to get height is arrived
Electric conductivity graphene film；
The graphene film/copper foil structure of composite membrane is copper foil and the graphene film being coated on the copper foil surface
Composite construction；
The polyacrylonitrile fibre membrane/copper foil composite membrane is that copper foil and the polyacrylonitrile being coated on the copper foil surface are fine
Tie up the composite construction of film.
In above-mentioned preparation method, the carrier gas can be the inert gases such as argon gas；
The flow of the carrier gas can be 500~1000sccm, preferably 500sccm；
The rate of the heating is 5~10 DEG C/min, preferably 10 DEG C/min；
Temperature after the heating is 300~600 DEG C, preferably 500 DEG C.
In above-mentioned preparation method, the time of the gas phase reaction can be 10~60 minutes, preferably 30 minutes.
In above-mentioned preparation method, the gas phase reaction carries out in low pressure CVD apparatus；
The vacuum degree of the vacuum condition is less than 5Pa.
In above-mentioned preparation method, the graphene film/copper foil structure of composite membrane and the polyacrylonitrile fibre membrane/copper
The distance between foil structure of composite membrane is preferably smaller than 1cm.
In above-mentioned preparation method, PAN (polyacrylonitrile) tunica fibrosa sets PAN reacting precursor as reacting precursor
In the graphene film/copper foil structure of composite membrane upstream, to be guaranteed at the graphene film in carrier gas downstream by effectively
Chemistry functional.
The method of the present invention is based on following principle: PAN (polyacrylonitrile) precursor cracks at a certain temperature forms active specy,
This active specy is carried to the graphene film in downstream by carrier gas, and carries out functional modification to graphene film.
It is thin in the surface of the copper foil growth graphene using chemical vapour deposition technique in above-mentioned preparation method
Film can be single-layer graphene；
The chemical vapour deposition technique can carry out under normal conditions, such as:
Select hydrogen as carrier gas, being passed through flow is 100~300sccm；
Select methane as carbon source gas, being passed through flow is 1~10sccm；
Growth temperature is 980 DEG C~1050 DEG C.
In above-mentioned preparation method, the polyacrylonitrile fibre is prepared on the surface of the copper foil using the method for electrostatic spinning
Film is tieed up, thickness can be 100nm~1000nm；
The electrostatic spinning can carry out under conditions of routine, such as:
Using DMF (dimethylformamide) solution of PAN, mass concentration is that the molecular weight of 6%~8%, PAN is
150000；
Spacing between spinning nozzle and the copper foil is 25~30cm；
Voltage is 15~20kV；
The spinning time is 3~10 minutes.
In above-mentioned preparation method, the thickness of the copper foil is preferably 18~50 μm.
The method of the present invention include thes steps that the high conductivity film that will be obtained is transferred in dielectric base；
It can specifically carry out in accordance with the following steps:
Polymethyl methacrylate (PMMA) is coated on the functionalization graphene film/copper foil being prepared, by copper foil
The functionalization graphene film that surface obtains is transferred on other dielectric bases (Si/SiOx substrate, glass, plastics etc.) surface；
Specifically used mass fraction is the ethyl lactate solution of 2~5%PMMA), being coated with rate is 1000~4000rpm, time 30
~60s then carries out the baking of 60s or more at 170 DEG C, can specifically toast 5~15min, is not less than the three of 1M using concentration
Acidic Ferric Chloride Solution or persulfate solution perform etching substrate copper foil as the etching agent of copper, etch period be 5~
30min obtains the graphene film supported by PMMA；The film is placed in other substrates and dries and removes PMMA using acetone
The graphene film in other dielectric bases can be obtained afterwards.
The high conductivity graphene film being prepared by the above method of the present invention also belongs to protection scope of the present invention.
" high conductivity " graphene film of the present invention refers to obtaining through " gas-phase chemical reaction " step of the invention
The graphene film that improves of electric conductivity.
The present invention has the advantage that
1, present invention process is simple and easy, and involved electrostatic spinning, low pressure chemical vapor deposition are all mature technologies.It is vapor-phase
It is very efficient and uniform to the functionalization of graphene film to learn reaction.
2, the electric conductivity of functionalization graphene film that the present invention obtains improves 40% or more, highly significant, and right
The translucency of graphene film influences very small.
Detailed description of the invention
Fig. 1 is the gas-phase chemical reaction schematic diagram of graphene film functionalization of the present invention.
Fig. 2 is the process unit schematic diagram that the method for the present invention uses.
Fig. 3 is SEM characterization and Raman characterization of the graphene film before and after gas-phase chemical reaction in the embodiment of the present invention 1.
Fig. 4 is electric conductivity (surface resistance) comparison of the graphene film before and after functionalization in the embodiment of the present invention 1.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The metallic substrates that graphene is grown in following embodiments use copper foil (AlfaAesar chemical company, purity
99.8%, 25 microns of thickness), before growing graphene, chemical polishing processing is carried out to copper foil.
Electrospun polymer uses DMF (dimethylformamide) solution of PAN (polyacrylonitrile) in following embodiments,
PAN molecular weight is 150000, and concentration of polymer solution is 6%~8%.
In following embodiments, copper foil etching liquid is the aqueous solution of the sodium peroxydisulfate of 0.2mol/L.
Graphene film before and after chemistry functional is characterized, morphology characterization, graphene including graphene film
The spectral property characterization of film and the electric conductivity of graphene film characterize.Measurement method is as follows:
The morphology characterization of graphene film: using the Lower mode of scanning electron microscope (Hitachi S-4800), (pattern is poor
It is different) it can significantly characterize pattern variation of the graphene film before and after functionalization.
The spectral property of graphene film characterizes: being measured using Raman spectrum (Horiba, JY800), it is thin to obtain graphene
Structural information before and after film chemical modification.
The electric conductivity of graphene film characterizes: using face resistance meter (CDE, Resmap) measurement obtains graphene
Surface resistance of the film before and after chemistry functional.
Embodiment 1, the chemistry functional method for improving graphene film electric conductivity
As shown in Figure 1, being the schematic diagram of the method for the present invention.
As shown in Fig. 2, being the process device figure of the method for the present invention, the specific steps are as follows:
1) in copper foil substrate graphene growth, using low-pressure chemical vapor deposition system (LPCVD).
By copper foil (purity 99.8%, 25 microns of thickness) at 1000 DEG C, first anneal 30 minutes under a hydrogen atmosphere, hydrogen stream
Amount is 300sccm, and system pressure is maintained at 350Pa, is then annealed 30 minutes, argon flow 500sccm under an argon, body
It is that pressure is maintained at 500Pa.The effect annealed under nitrogen atmosphere is to restore the oxide layer of copper foil surface, the effect annealed under argon atmospher
It is the active nucleation site for reducing copper foil surface, improves the crystal domain size of graphene film.After the completion of process annealed above, continue
The growth of graphene film is carried out at 1000 DEG C, condition is 200sccm hydrogen+1sccm methane (carbon-source gas), growth time
It is 1 hour.Finally growth obtains graphene film on copper foil, with a thickness of single layer.
2) PAN spinning fibre film is made in another naked copper foil surface.
Naked copper foil is placed on the cathode sample stage of electrostatic spinning, the positive spray head of electrostatic spinning is placed in the upper of naked copper foil
About 25 centimeters of side, it is the DMF solution of 150000 PAN, concentration 8% that spinning macromolecule, which selects molecular weight,.When electrostatic spinning
Add 15kV voltage, the spinning time is 5 minutes, ultimately form PAN fiber film/copper foil, wherein PAN fiber film with a thickness of 200nm.
3) as shown in the process device figure in Fig. 2, two samples of PAN fiber film/copper foil and graphene/copper foil are successively set
In the quartz chamber body of low pressure chemical vapor deposition, wherein PAN fiber film/copper foil is in the upstream of carrier gas stream, and graphene/copper foil is located next to
Downstream in carrier gas stream (spacing between the two is 1mm).After closing cavity, 5Pa is evacuated to hereinafter, being passed through
The argon gas (Ar) of 500sccm, rises to 500 DEG C for quartz chamber body temperature with the heating rate of 10 DEG C/min, then in this temperature and
Gas phase reaction is carried out under the above argon carrier flow, the reaction time is 30 minutes.It is naturally cooling to room temperature after the reaction was completed, opens
Quartz chamber body takes out sample, carries out a series of characterizations.
4) graphene film of above-mentioned completion chemistry functional is transferred to Si/SiOx dielectric base from copper foil substrate
On, detailed process is as follows:
By the above-mentioned spin coating polymethyl methacrylate (PMMA) from the graphene film/copper foil taken out in quartz chamber body,
Specifically used mass fraction be 6%PMMA ethyl lactate solution, spin coating rate be 4000rpm, spin-coating time 60s, then
By the baking of PMMA spin-coating film progress 3 minutes at 170 DEG C.Copper foil substrate is performed etching using copper foil etching liquid, when etching
Between be 30min, after obtain the graphene film supported by PMMA, which is placed in Si/SiOx substrate and is dried and using third
The graphene film of chemistry functional can be transferred in dielectric base after ketone removal PMMA.
Characterization is measured to the graphene film of chemistry functional below:
The morphology characterization of graphene film: being the SEM figure in the graphene single crystal domains area just grown, figure as shown in Fig. 3 a)
3b) be the later graphene single crystal domains area of chemistry functional SEM figure, from front and back comparison as can be seen that graphene vapor-phase
It learns reaction and still maintains pattern integrality later, while can see the graphene surface after reaction and becoming rougher.
The spectral property of graphene film characterizes: being the graphene film for not carrying out gas-phase chemical reaction as shown in Fig. 3 c)
Raman spectrum, it can be seen that almost without the presence of the peak D, and 2D peak intensity/peak intensity > 2 G, so this graphene film is
Defect concentration is very low, the good high quality monolayer graphene of crystallization degree.Fig. 3 d) it is that graphene after gas-phase chemical reaction is thin
The Raman spectrum of film, it can be seen that the strong peak D illustrates that the graphene film of chemistry functional introduces many defects, while 2D
Peak maintains stronger signal, illustrates that the lattice structure of graphene film keeps complete.
The electric conductivity of graphene film characterizes: if Fig. 4 a) illustrates the electric conductivity of original graphite alkene film, to multiple
The sample of sample (repeat the above steps 1) preparation) retest discovery is carried out, the surface resistance of original graphite alkene film is
872Ω/□.Fig. 4 b) electric conductivity of functionalization graphene film by gas-phase chemical reaction of the invention is illustrated, it is multiple
Sample (repeat the above steps 1) -4) preparation sample) retest the results show that its surface resistance is 510 Ω/, lead
Electrical property improves 40% or more, highly significant.
Claims (7)
1. a kind of preparation method of high conductivity graphene film, includes the following steps:
Along the airflow direction of carrier gas, by polyacrylonitrile fibre membrane/copper foil structure of composite membrane and graphene film/copper foil composite membrane knot
Structure is sequentially placed into quartz chamber body, is passed through the carrier gas and is warming up to 300~600 DEG C, carries out gas phase reaction under vacuum conditions,
Obtain high conductivity graphene film；
The graphene film/copper foil structure of composite membrane is copper foil and the graphene film that is coated on the copper foil surface is answered
Close structure；
The polyacrylonitrile fibre membrane/copper foil composite membrane is copper foil and the polyacrylonitrile fibre membrane being coated on the copper foil surface
Composite construction.
2. preparation method according to claim 1, it is characterised in that: the carrier gas is inert gas；
The flow of the carrier gas is 500~1000sccm；
The rate of the heating is 5~10 DEG C/min.
3. preparation method according to claim 1 or 2, it is characterised in that: the time of the gas phase reaction is 10~60 points
Clock.
4. preparation method according to claim 3, it is characterised in that: the gas phase reaction carries out in low pressure CVD apparatus；
The vacuum degree of the vacuum condition is less than 5Pa.
5. the preparation method according to claim 4, it is characterised in that: using chemical vapour deposition technique the copper foil table
Length of the looking unfamiliar graphene film.
6. preparation method according to claim 5, it is characterised in that: using electrostatic spinning method the copper foil table
Wheat flour is for the polyacrylonitrile fibre membrane.
7. the high conductivity graphene film of any one of claim 1-6 the method preparation.
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| DE102009049379A1 (en) * | 2009-10-15 | 2011-04-21 | Bayer Technology Services Gmbh | Composite materials with graphene layers and their preparation and use |
| WO2016025532A1 (en) * | 2014-08-11 | 2016-02-18 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Aligned graphene-carbon nanotube porous carbon composite |
| CN104269516B (en) * | 2014-10-11 | 2016-08-17 | 南京中储新能源有限公司 | A kind of secondary cell anode composite based on vertical orientated Graphene |
| CN104651802A (en) * | 2015-01-19 | 2015-05-27 | 重庆大学 | Method for directly synthesising nitrogen-doped graphene by simply using solid nitrogen source |
| CN104979038B (en) * | 2015-06-08 | 2018-04-06 | 北京大学 | Topological insulator/graphene composite and flexible transparent conductive film and preparation method and application |
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