CN108706574A - A method of the copper-based multi-layer graphene of growth - Google Patents
A method of the copper-based multi-layer graphene of growth Download PDFInfo
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- CN108706574A CN108706574A CN201810759667.8A CN201810759667A CN108706574A CN 108706574 A CN108706574 A CN 108706574A CN 201810759667 A CN201810759667 A CN 201810759667A CN 108706574 A CN108706574 A CN 108706574A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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Abstract
The invention discloses a kind of methods of the copper-based multi-layer graphene of growth, include the following steps：(1) it is put into holder after being pre-processed to copper foil substrate；(2) one layer of metal foil is coated in the outside of holder；(3) holder of above-mentioned cladding metal foil vacuum system is put into make annealing treatment；(4) it is passed through carbonaceous gas reaction 30-60min, multi-layer graphene is formed on the surface of copper foil after cooling.The present invention using low pressure gas phase deposition method due to growing copper-base graphite alkene, and safety is good, the speed of growth is fast；The catalytic decomposition efficiency to carbonaceous gas can be improved by coating one layer of metal foil in the outside of holder, so that the concentration of carbon atom is increased, while inhibiting the evaporation of copper foil substrate, contributed to form multi-layer graphene.Operation is simple for method using the present invention, external sheath metal foil may be reused, and does not increase energy consumption additionally, can form the graphene of high quality, high multilayer rate.
Description
Technical field
The present invention relates to graphene films to grow preparation field, and in particular to one kind growing Multi-layer graphite on metal copper foil
The method of alkene.
Background technology
Graphene refers to that carbon atom is arranged with sp2 hybridized orbits in honeycomb lattice (honeycomb crystal lattice)
Arrange the single layer two dimensional crystal constituted.Graphene world market sustainable growth in recent years is expected to be more than current all nano materials,
Especially in consumption electronic product and energy stores application aspect.
Currently, chemical vapor deposition (CVD) method is widely used in the preparation of graphene film, there is simple, easy to operate, ruler
It is very little big and the advantages that be easily transferred in other substrates.Using polycrystalline copper foil as catalyst, at a high temperature of 1000 DEG C or more
The features such as graphene of growth has resistivity low, and the speed of electron transfer is fast.However although having very high mobility, zero
The Half-metallic of band gap limits application of the graphene in semiconductor applications.Studies have shown that two or more layers graphene, Ke Yitong
Application outfield or strain are crossed, band gap is opened while ensureing intrinsic excellent properties, may be used on such as semiconductor and display element
The fields such as the wiring of equal electronic components or metal surface coating film.
The general bilayer or multilayer graphene that obtains is that the single-layer graphene for synthesizing chemical vapour deposition technique shifts two repeatedly
It is secondary or multiple, however, this method complex process and take, transfer process be difficult to control, easily cause graphene damage and foreign matter
Residual.Therefore the method for developing direct synthesizing multilayer graphene is needed.Chinese Patent Application No. be 201410725258.8 it is special
In profit, the method using high temperature argon method assisting growth multi-layer graphene is disclosed.This method uses stage growth, is being formed
After first layer graphene, lead to the argon gas of a period of time at high temperature, then carries out the growth of the second layer.This method growth cycle
Long, high energy consumption, the graphene size grown is smaller, limits its scope of application.China Patent Publication No. CN106835260,
Publication date on June 13rd, 2017, the entitled oversize multilayer single crystal graphene and large size single crystal cupro-nickel of innovation and creation close
The preparation method of gold, this application discloses in single crystal Cu nickel plating carry out the growth of multi-layer graphene.Single crystal Cu valence first
Lattice are high, it is difficult to obtain and generally use, secondly nickel plating also further increases cost in single crystal Cu, and the thickness of nickel plating can influence
The number of plies and quality of graphene.
Invention content
It uses metal copper foil as catalytic substrate the technical problem to be solved in the present invention is to provide a kind of, grows Multi-layer graphite
The method of alkene.
In order to solve the above-mentioned technical problem, the technical scheme is that：
A method of the copper-based multi-layer graphene of growth includes the following steps：
(1) it is put into holder after being pre-processed to copper foil substrate；
(2) one layer of metal foil is coated in the outside of holder；
(3) holder of above-mentioned cladding metal foil vacuum system is put into make annealing treatment；
(4) it is passed through carbonaceous gas reaction 30-60min, multi-layer graphene is formed on the surface of copper foil after cooling.
Preferably, the pretreatment in the step (1) refer to chemical reagent processing, polishing treatment, electroplating processes, at spraying
At least one of reason, laser treatment, corona treatment or electron beam treatment.
Preferably, the metal foil in the step (2) is nickel (Ni) foil, cobalt (Co) foil, iron (Fe) foil, gold (Au) foil, aluminium
(Al) foil, chromium (Cr) foil, platinum (Pt) foil, magnesium (Mg) foil, manganese (Mn) foil, molybdenum (Mo) foil, ruthenium (Rh) foil, tantalum (Ta) foil, titanium (Ti)
At least one of foil or tungsten (W) foil.
Preferably, the annealing in the step (3) is：The holder for coating metal foil is passed through 1- in a low pressure environment
The inertia or reducibility gas of 100SCCM is heated to 800-1100 DEG C, keeps 10-120min.
Preferably, the inertia or reducibility gas include at least one of hydrogen, nitrogen, argon gas, helium or neon.
Preferably, the carbonaceous gas in the step (4) include methane, it is ethane, ethylene, acetylene, propane, n-butene, different
At least one of butylene, 1,3- butadiene, normal butane, iso-butane, propylene or cyclopropane.
Beneficial effects of the present invention：Using above-mentioned technical proposal, due to growing copper-base graphite using low pressure gas phase deposition method
Alkene, safety is good, the speed of growth is fast；The catalytic decomposition to carbonaceous gas can be improved by coating one layer of metal foil in the outside of holder
Efficiency makes the concentration of carbon atom increase, while inhibiting the evaporation of copper foil substrate, contributes to form multi-layer graphene.Using this hair
Operation is simple for bright method, external sheath metal foil may be reused, and does not increase energy consumption additionally, can be formed high quality,
The graphene of high multilayer rate.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of the multi-layer graphene arrived prepared by method using the present invention；
Fig. 2 is the Raman spectrograms of the bilayer graphene arrived prepared by method using the present invention；
Fig. 3 is the Raman spectrograms of the multi-layer graphene arrived prepared by method using the present invention.
Specific implementation mode
The specific implementation mode of invention is described further below in conjunction with the accompanying drawings.It should be noted that for this
The explanation of a little embodiments is used to help understand the present invention, but does not constitute limitation of the invention.In addition, disclosed below
Involved technical characteristic can be combined with each other as long as they do not conflict with each other in each embodiment of the present invention.
Embodiment 1
A method of the copper-based multi-layer graphene of growth：The copper foil that it is 99.8% to take purity, thickness is 25 microns, is put into throwing
In light liquid, polished 60 seconds under 5V voltages.Copper foil after polishing is taken out, is put into and is cleaned 3 times and dry up in ethyl alcohol.After handling
Copper foil be put into quartz holder.
It is 18 microns of copper foil to take another thickness, is cleaned with EtOH Sonicate.This copper foil is carefully wrapped in quartz holder
Outside, be then placed in the center of atmosphere tube type stove.The argon gas for leading to a period of time into tube furnace, is then shut off.Again to tubular type
Lead to hydrogen in stove and be heated to 800 DEG C and anneals 120 minutes.Continue to be passed through methane, keeps stopping heating after sixty minutes, wait for tube furnace
It is cooled to room temperature taking-up quartz holder.The graphene being grown on copper foil is characterized with scanning electron microscope and Raman spectrometer.
It is more than 80% using the graphene bilayer rate that this method is prepared, graphene multilayer rate is more than 50%, the multilayer being prepared
Graphene is the continuous film that graphene monocrystalline is spliced into.
Embodiment 2
A method of the copper-based multi-layer graphene of growth：The copper foil that it is 99.8% to take purity, thickness is 35 microns, is put into throwing
In light liquid, polished 60 seconds under 5V voltages.Copper foil after polishing is taken out, is put into and is cleaned 3 times and dry up in ethyl alcohol.After handling
Copper foil be put into quartz holder.
It is 18 microns of nickel foil to take another thickness, is cleaned with EtOH Sonicate.This nickel foil is carefully wrapped in quartz holder
Outside, be then placed in the center of atmosphere tube type stove.
The nitrogen for leading to a period of time into pipe, is then shut off.Lead to hydrogen into pipe again and be heated to 1100 DEG C and anneals 10 points
Clock.Continue to be passed through ethylene, stops heating after being kept for 30 minutes, wait for that tube furnace is cooled to room temperature taking-up quartz holder.With scanning electricity
Mirror and Raman spectrometer characterize the graphene being grown on copper foil.The graphene bilayer rate being prepared using this method
More than 80%, graphene multilayer rate is more than 50%, and the multi-layer graphene being prepared is spliced into continuous thin for graphene monocrystalline
Film.
As shown in Figure 1, the scanning electron microscope diagram of the multi-layer graphene arrived prepared for method using the present invention, it can
To find out the graphene film that even compact is prepared.As shown in Fig. 2, the bilayer arrived prepared for method using the present invention
The Raman spectrograms of graphene, it can be seen that be located at 1580cm-1The more sharp characteristic peak at left and right place and positioned at 2700cm-1
The strong and sharp characteristic peak of left and right.As shown in figure 3, being the multi-layer graphene arrived prepared by method using the present invention
Raman spectrograms, it can be seen that be located at 1580cm-1The characteristic peak at left and right place will obviously by force and sharply in bilayer graphene structure,
This feature peak energy reacts the number of plies of graphene, illustrates that the graphene-structured is multilayer, and be located at 2700cm-1The characteristic peak of left and right is wanted
Weak and delay in bilateral graphene-structured, it is multilayered structure to demonstrate this graphene.
Embodiments of the present invention are explained in detail above in association with attached drawing, but the present invention is not limited to described implementations
Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments
A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.
Claims (6)
1. a kind of method of the copper-based multi-layer graphene of growth, it is characterised in that：Include the following steps：
(1) it is put into holder after being pre-processed to copper foil substrate；
(2) one layer of metal foil is coated in the outside of holder；
(3) holder of above-mentioned cladding metal foil vacuum system is put into make annealing treatment；
(4) it is passed through carbonaceous gas reaction 30-60min, multi-layer graphene is formed on the surface of copper foil after cooling.
2. the method for the copper-based multi-layer graphene of growth according to claim 1, it is characterised in that：In the step (1)
Pretreatment refers to chemical reagent processing, polishing treatment, electroplating processes, spray treatment, laser treatment, corona treatment or electronics
At least one of beam processing.
3. the method for the copper-based multi-layer graphene of growth according to claim 1, it is characterised in that：In the step (2)
Metal foil is nickel (Ni) foil, cobalt (Co) foil, iron (Fe) foil, gold (Au) foil, aluminium (Al) foil, chromium (Cr) foil, platinum (Pt) foil, magnesium (Mg)
At least one of foil, manganese (Mn) foil, molybdenum (Mo) foil, ruthenium (Rh) foil, tantalum (Ta) foil, titanium (Ti) foil or tungsten (W) foil.
4. the method for the copper-based multi-layer graphene of growth according to claim 1, it is characterised in that：In the step (3)
Annealing is：The holder for coating metal foil is passed through to the inertia or reducibility gas of 1-100SCCM in a low pressure environment, is heated
To 800-1100 DEG C, 10-120min is kept.
5. the method for the copper-based multi-layer graphene of growth according to claim 4, it is characterised in that：The inertia or reproducibility
Gas includes at least one of hydrogen, nitrogen, argon gas, helium or neon.
6. the method for the copper-based multi-layer graphene of growth according to claim 1, it is characterised in that：In the step (4)
Carbonaceous gas include methane, ethane, ethylene, acetylene, propane, n-butene, isobutene, 1,3- butadiene, normal butane, iso-butane,
At least one of propylene or cyclopropane.
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| CN201810759667.8A CN108706574A (en) | 2018-07-11 | 2018-07-11 | A method of the copper-based multi-layer graphene of growth |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485035A (en) * | 2018-11-12 | 2019-03-19 | 南京大学 | A kind of double-deck or three layers of graphene preparation method |
| CN114213706A (en) * | 2021-12-02 | 2022-03-22 | 北京石墨烯技术研究院有限公司 | Graphene composite material, preparation method thereof, heat dissipation member and electronic device |
| CN116397211A (en) * | 2023-03-27 | 2023-07-07 | 哈尔滨理工大学 | Method for preparing multilayer graphene based on chemical vapor deposition method |
-
2018
- 2018-07-11 CN CN201810759667.8A patent/CN108706574A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485035A (en) * | 2018-11-12 | 2019-03-19 | 南京大学 | A kind of double-deck or three layers of graphene preparation method |
| CN114213706A (en) * | 2021-12-02 | 2022-03-22 | 北京石墨烯技术研究院有限公司 | Graphene composite material, preparation method thereof, heat dissipation member and electronic device |
| CN116397211A (en) * | 2023-03-27 | 2023-07-07 | 哈尔滨理工大学 | Method for preparing multilayer graphene based on chemical vapor deposition method |
| CN116397211B (en) * | 2023-03-27 | 2024-01-16 | 哈尔滨理工大学 | Method for preparing multilayer graphene based on chemical vapor deposition method |
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