CN106744864B - A kind of preparation method of the bicyclic graphene nano structure of hexagon - Google Patents
A kind of preparation method of the bicyclic graphene nano structure of hexagon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 23
- 125000002619 bicyclic group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011889 copper foil Substances 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005530 etching Methods 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- 239000005751 Copper oxide Substances 0.000 claims description 32
- 229910000431 copper oxide Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003708 ampul Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007781 pre-processing Methods 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 239000012159 carrier gas Substances 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 9
- 238000002003 electron diffraction Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention discloses a kind of preparation methods of the bicyclic graphene nano structure of hexagon, pass through chemical vapour deposition technique, with methane, ethylene is carbon source, hydrogen is reducibility gas, inert gas is carrier gas, copper foil is as substrate, crack carbon source at high temperature, and the surface under the catalytic action of copper foil in copper foil grows graphene, and utilize growth, etching, regrowth and the technical solution etched again are prepared with the bicyclic graphene nano structure of hexagon, technical solution of the present invention preparation process is simple, it provides to design the graphene nano structure of special construction and very important instructs thinking, it has been also equipped with good promotion and application value simultaneously.
Description
Technical field
The present invention relates to graphene preparation method field, the preparation of especially a kind of bicyclic graphene nano structure of hexagon
Method.
Background technique
Graphene is that one kind is made of carbon atom, with sp2Hybridized orbit forms the two dimensional crystal that hexangle type is in honeycomb lattice,
Because its power, heat, light, in terms of shown excellent properties due to cause the great interest of scientific research personnel.Currently, graphite
The preparation method of alkene has very much, such as mechanical stripping method, oxidation-reduction method, silicon carbide epitaxial growth method, chemical vapour deposition technique
Deng.In these methods, interlayer stack orientation is clear, marginal texture is clear, different because it can be prepared for chemical vapour deposition technique
The graphene of the special spaces structure such as shape and receive more and more attention.Since the performance of graphene has with its space structure
Close relationship, therefore, preparation, which grows the graphene of special space structure, becomes current conventional chemical vapor sedimentation
The important research direction of graphene is prepared on copper foil, this has great importance to the application for accelerating graphene, still, realizes
The controllable growth of graphene specific shape and structure still suffers from very big challenge, and not requiring nothing more than has fine control to growth conditions
System, but also require to be formed with the growth machine of graphene deep understanding.
Summary of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to be directed to existing chemical vapour deposition technique on copper foil
The graphene of special construction is prepared there are still insufficient problem is utilized and understood to its growth mechanism, a kind of application value is provided
The preparation method of high, the easy to operate bicyclic graphene nano structure of simple hexagon.
In order to realize above-mentioned technical purpose, the technical solution of the present invention is as follows:
A kind of preparation method of the bicyclic graphene nano structure of hexagon comprising following steps:
1) using copper foil as graphene growth substrate, copper foil is put into the quartz ampoule of tube furnace, then with 280~
The flow of 320sccm is continually fed into inert gas, and the temperature of tube furnace is set as 1040~1100 DEG C, when tube furnace is warming up to
After set temperature, maintain temperature constant, then be passed through hydrogen with the flow of 45~55sccm, under the atmosphere of inert gas and hydrogen
2.5~3.5h of annealing is carried out, copper foil surface is made to generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained at 1040~1100 DEG C, and under the conditions of the temperature, stopped logical
Enter inert gas, using the copper oxide nanometer particle on copper foil as nucleating point, gaseous carbon sources be passed through with the flow of 0.4~0.6sccm,
And the flow for being passed through hydrogen is adjusted to 95~105sccm, cracks carbon source under high temperature action, then urging in copper foil
Graphene is grown in copper foil surface under change effect, maintenance system condition simultaneously carries out 30~60min of graphene growth；
3) step 2 growth after, with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm, performs etching 60~120min by 0.6sccm；
4) after etching, then using copper oxide nanometer particle as growing point, keep the flow of gaseous carbon sources be 0.4~
The flow of hydrogen is adjusted to 95~105sccm, carries out 10~20min of graphene regrowth by 0.6sccm；
5) step 4) growth after, then with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm again, then performs etching 5~15min by 0.6sccm；
6) step 5) etching after, stopping be passed through gaseous carbon sources, cool down to tube furnace, in temperature-fall period continue with
The flow of 280~320sccm is passed through inert gas, is passed through hydrogen with the flow of 3~5sccm, is cooled to room temperature to tube furnace, i.e.,
It is obtained to grow the graphene for having twin nuclei.
Further, the step 1) further includes pre-processing before copper foil is put into tube furnace to copper foil, described
Preprocessing process are as follows: copper foil is put into dilute hydrochloric acid and is cleaned by ultrasonic, then transfers in acetone soln and carries out ultrasound clearly
It washes, is dried up after cleaning with high pressure nitrogen.
Further, the inert gas of the step 1) and step 6) is argon gas, helium or neon.
Further, the gaseous carbon sources that the step 2) is passed through are methane, ethylene.
Further, the set temperature of the step 1) tube furnace is 1070 DEG C.
Further, step 2 set temperature of tube furnace into step 5) is 1070 DEG C.
Further, step 2 flow of gaseous carbon sources into step 5) is 0.5sccm.
Further, it is 100sccm that the hydrogen of the step 2 and step 4), which is passed through flow, the step 3) and step 5)
It is 3sccm that hydrogen, which is passed through flow,.
Using above-mentioned technical solution, the invention has the benefit that by chemical vapour deposition technique, with methane, ethylene
For carbon source, hydrogen and inert gas are as carrier gas, and copper foil first pre-processes copper foil surface as substrate, then in high temperature
Under the conditions of anneal, copper oxide nanometer particle is formed on its surface, using copper oxide nanometer particle as nucleating point and etching
The double action of point, is regulated and controled by the flow that is passed through to hydrogen, realizes the control to graphene growth or etching process, most
The graphene with hexagon twin nuclei is obtained eventually, and this method preparation process is simple, receives to design the graphene of special construction
Rice structure provide it is very important instruct thinking, while this method also has good promotion prospect and application value.
Detailed description of the invention
The present invention is further elaborated with reference to the accompanying drawings and detailed description:
Fig. 1 is the schematic diagram of hexagon monocycle graphene nano structure；
Fig. 2 is the schematic diagram of the bicyclic graphene nano structure of hexagon of the present invention；
Fig. 3 is the schematic arrangement of the bicyclic graphene of hexagon of the present invention；
Fig. 4 is that the bicyclic graphene nano structure of hexagon prepared by the embodiment of the present invention 1 is transferred under silicon dioxide liner
Electron-microscope scanning figure；
Fig. 5 is corresponding Raman spectrogram at A, B in Fig. 4；
Fig. 6 is the electronic diffraction schematic diagram of the bicyclic graphene nano structure of hexagon prepared by the embodiment of the present invention 1；
Fig. 7 is the electron diffraction diagram in Fig. 6 at 1；
Fig. 8 is the electron diffraction diagram in Fig. 6 at 2；
Fig. 9 is the electron diffraction diagram in Fig. 6 at 3；
Figure 10 is the electron diffraction diagram in Fig. 6 at 4；
Figure 11 is the electron diffraction diagram in Fig. 6 at 5；
Figure 12 is the electron diffraction diagram in Fig. 6 at 6.
Specific embodiment
A kind of preparation method of the bicyclic graphene nano structure of hexagon comprising following steps:
1) using copper foil as graphene growth substrate, copper foil is put into the quartz ampoule of tube furnace, then with 280~
The flow of 320sccm is continually fed into inert gas, and the temperature of tube furnace is set as 1040~1100 DEG C, when tube furnace is warming up to
After set temperature, maintain temperature constant, then be passed through hydrogen with the flow of 45~55sccm, under the atmosphere of inert gas and hydrogen
2.5~3.5h of annealing is carried out, copper foil surface is made to generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained at 1040~1100 DEG C, and under the conditions of the temperature, stopped logical
Enter inert gas, using the copper oxide nanometer particle on copper foil as nucleating point, gaseous carbon sources be passed through with the flow of 0.4~0.6sccm,
And the flow for being passed through hydrogen is adjusted to 95~105sccm, cracks carbon source under high temperature action, then urging in copper foil
Graphene is grown in copper foil surface under change effect, maintenance system condition simultaneously carries out 30~60min of graphene growth；
3) step 2 growth after, with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm, performs etching 60~120min by 0.6sccm；
4) after etching, then using copper oxide nanometer particle as growing point, keep the flow of gaseous carbon sources be 0.4~
The flow of hydrogen is adjusted to 95~105sccm, carries out 10~20min of graphene regrowth by 0.6sccm；
5) step 4) growth after, then with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm again, then performs etching 5~15min by 0.6sccm；
6) step 5) etching after, stopping be passed through gaseous carbon sources, cool down to tube furnace, in temperature-fall period continue with
The flow of 280~320sccm is passed through inert gas, is passed through hydrogen with the flow of 3~5sccm, is cooled to room temperature to tube furnace, i.e.,
It is obtained to grow the graphene for having twin nuclei.
Further, the step 1) further includes pre-processing before copper foil is put into tube furnace to copper foil, described
Preprocessing process are as follows: copper foil is put into dilute hydrochloric acid and is cleaned by ultrasonic, then transfers in acetone soln and carries out ultrasound clearly
It washes, is dried up after cleaning with high pressure nitrogen.
Further, the inert gas of the step 1) and step 6) is argon gas, helium or neon.
Further, the gaseous carbon sources that the step 2) is passed through are methane, ethylene.
Further, the set temperature of the step 1) tube furnace is 1070 DEG C.
Further, step 2 set temperature of tube furnace into step 5) is 1070 DEG C.
Further, step 2 flow of gaseous carbon sources into step 5) is 0.5sccm.
Further, it is 100sccm that the hydrogen of the step 2 and step 4), which is passed through flow, the step 3) and step 5)
It is 3sccm that hydrogen, which is passed through flow,.
Embodiment 1
A kind of preparation method of the bicyclic graphene nano structure of hexagon comprising following steps:
1) copper foil that interception size is 2.5cmX2.5cm is as graphene growth substrate, by copper foil be put into dilute hydrochloric acid into
Row ultrasonic cleaning, then transfers in acetone soln and is cleaned by ultrasonic, dried up after cleaning with high pressure nitrogen, then by copper
Foil is put into the quartz ampoule of tube furnace, is then continually fed into argon gas with the flow of 300sccm, and the temperature of tube furnace is set as
1070 DEG C, when tubular type furnace temperature rises to 1070 DEG C, maintain temperature constant, then be passed through hydrogen with the flow of 50sccm, in argon
High annealing 3h is carried out under the atmosphere of gas and hydrogen, and copper foil surface is made to generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained 1070 DEG C, under the conditions of the temperature, stopping is passed through argon gas,
Using the copper oxide nanometer particle on copper foil as nucleating point, methane, and the flow tune that hydrogen is passed through are passed through with the flow of 0.5sccm
Section is 100sccm, and the carbon source for carrying methane cracks under high temperature action, then in copper foil under the catalytic action of copper foil
Surface grows graphene, maintenance system condition, and carries out graphene growth 30min；
3) after growing, maintaining tubular type furnace temperature is 1070 DEG C, is etching point with copper oxide nanometer particle, keeps methane
Flow be 0.5sccm, the flow of hydrogen is adjusted to 3sccm, performs etching 120min；
4) after etching, maintaining tubular type furnace temperature is 1070 DEG C, then using copper oxide nanometer particle as growing point, keeps first
The flow of alkane is 0.5sccm, and the flow of hydrogen is adjusted to 100sccm, carries out graphene regrowth 15min；
5) after step 4) growth, maintaining tubular type furnace temperature is 1070 DEG C, then with copper oxide nanometer particle to etch point,
Holding methane flow is 0.5sccm, the flow of hydrogen is adjusted to 3sccm again, then perform etching 10min；
6) after step 5) etching, cool down to tube furnace, continue to be passed through argon with 300sccm flow in temperature-fall period
Gas is passed through hydrogen with 4sccm flow, is cooled to room temperature to tube furnace, obtains the graphene that growth has twin nuclei.
Embodiment 2
A kind of preparation method of the bicyclic graphene nano structure of hexagon comprising following steps:
1) copper foil that interception size is 2.5cmX2.5cm is as graphene growth substrate, by copper foil be put into dilute hydrochloric acid into
Row ultrasonic cleaning, then transfers in acetone soln and is cleaned by ultrasonic, dried up after cleaning with high pressure nitrogen, then by copper
Foil is put into the quartz ampoule of tube furnace, is then continually fed into helium with the flow of 320sccm, and the temperature of tube furnace is set as
1040 DEG C, when tubular type furnace temperature rises to 1040 DEG C, maintain temperature constant, then be passed through hydrogen with the flow of 45sccm, in helium
High annealing 3.5h is carried out under the atmosphere of gas and hydrogen, and copper foil surface is made to generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained 1040 DEG C, under the conditions of the temperature, stopping is passed through helium,
Using the copper oxide nanometer particle on copper foil as nucleating point, ethylene, and the flow tune that hydrogen is passed through are passed through with the flow of 0.6sccm
Section is 105sccm, and the carbon source for carrying ethylene cracks under high temperature action, then in copper foil under the catalytic action of copper foil
Surface grows graphene, maintenance system condition, and carries out graphene growth 45min；
3) after growing, maintaining tubular type furnace temperature is 1040 DEG C, is etching point with copper oxide nanometer particle, keeps ethylene
Flow be 0.6sccm, the flow of hydrogen is adjusted to 3.5sccm, performs etching 90min；
4) after etching, maintaining tubular type furnace temperature is 1040 DEG C, then using copper oxide nanometer particle as growing point, keeps second
The flow of alkene is 0.6sccm, and the flow of hydrogen is adjusted to 105sccm, carries out graphene regrowth 10min；
5) after step 4) growth, maintaining tubular type furnace temperature is 1040 DEG C, then with copper oxide nanometer particle to etch point,
Holding ethene flow is 0.6sccm, the flow of hydrogen is adjusted to 3.5sccm again, then perform etching 5min；
6) after step 5) etching, cool down to tube furnace, continue to be passed through helium with 280sccm flow in temperature-fall period
Gas is passed through hydrogen with 5sccm flow, is cooled to room temperature to tube furnace, obtains the graphene that growth has twin nuclei.
Embodiment 3
A kind of preparation method of the bicyclic graphene nano structure of hexagon comprising following steps:
1) copper foil that interception size is 2.5cmX2.5cm is as graphene growth substrate, by copper foil be put into dilute hydrochloric acid into
Row ultrasonic cleaning, then transfers in acetone soln and is cleaned by ultrasonic, dried up after cleaning with nitrogen, then by copper
Foil is placed in tungsten boat in the quartz ampoule for being put into tube furnace, is then continually fed into neon with the flow of 280sccm, and by tube furnace
Temperature is set as 1100 DEG C, when tubular type furnace temperature rises to 1100 DEG C, maintains temperature constant, then be passed through hydrogen with the flow of 55sccm
Gas carries out high annealing 2.5h under the atmosphere of neon and hydrogen, and copper foil surface is made to generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained 1100 DEG C, under the conditions of the temperature, stopping is passed through neon,
Using the copper oxide nanometer particle on copper as nucleating point, methane is passed through with the flow of 0.4sccm, and the flow that hydrogen is passed through is adjusted
For 95sccm, the carbon source for carrying methane cracks under high temperature action, then in copper foil surface under the catalytic action of copper
Graphene, maintenance system condition are grown, and carries out graphene growth 60min；
3) after growing, maintaining tubular type furnace temperature is 1100 DEG C, is etching point with copper oxide nanometer particle, keeps methane
Flow be 0.4sccm, the flow of hydrogen is adjusted to 2.5sccm, performs etching 60min；
4) after etching, maintaining tubular type furnace temperature is 1100 DEG C, then using copper oxide nanometer particle as growing point, keeps first
The flow of alkane is 0.4sccm, and the flow of hydrogen is adjusted to 95sccm, carries out graphene regrowth 20min；
5) after step 4) growth, maintaining tubular type furnace temperature is 1100 DEG C, then with copper oxide nanometer particle to etch point,
Holding methane flow is 0.4sccm, the flow of hydrogen is adjusted to 2.5sccm again, then perform etching 15min；
6) after step 5) etching, cool down to tube furnace, continue to be passed through helium with 320sccm flow in temperature-fall period
Gas is passed through hydrogen with 3sccm flow, is cooled to room temperature to tube furnace, obtains the graphene that growth has twin nuclei.
The above is the embodiment of the present invention, for the ordinary skill in the art, religion according to the present invention
Lead, without departing from the principles and spirit of the present invention all equivalent changes done according to scope of the present invention patent, repair
Change, replacement and variant, is all covered by the present invention.
Claims (7)
1. a kind of preparation method of the bicyclic graphene nano structure of hexagon, it is characterised in that: itself the following steps are included:
1) using copper foil as graphene growth substrate, copper foil is put into the quartz ampoule of tube furnace, then with 280~320sccm
Flow be continually fed into inert gas, and the temperature of tube furnace is set as 1040~1100 DEG C, when tube furnace is warming up to setting temperature
After degree, maintains temperature constant, then be passed through hydrogen with the flow of 45~55sccm, moved back under the atmosphere of inert gas and hydrogen
2.5~3.5h of fire makes copper foil surface generate copper oxide nanometer particle；
2) after the completion of annealing, the temperature of tube furnace is maintained at 1040~1100 DEG C, and under the conditions of the temperature, stopping is passed through lazy
Property gas using the copper oxide nanometer particle on copper foil as nucleating point gaseous carbon sources are passed through with the flow of 0.4~0.6sccm, and will
The flow that hydrogen is passed through is adjusted to 95~105sccm, cracks carbon source under high temperature action, then makees in the catalysis of copper foil
Graphene is grown in copper foil surface under, maintenance system condition simultaneously carries out 30~60min of graphene growth, wherein gaseous carbon
Source is methane or ethylene；
3) step 2 growth after, with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm, performs etching 60~120min by 0.6sccm；
4) after etching, then using copper oxide nanometer particle as growing point, keeping the flow of gaseous carbon sources is 0.4~0.6sccm,
The flow of hydrogen is adjusted to 95~105sccm, carries out 10~20min of graphene regrowth；
5) step 4) growth after, then with copper oxide nanometer particle be etching point, keep gaseous carbon sources flow be 0.4~
The flow of hydrogen is adjusted to 2.5~3.5sccm again, then performs etching 5~15min by 0.6sccm；
6) after step 5) etching, stopping is passed through gaseous carbon sources, cools down to tube furnace, continues in temperature-fall period with 280
The flow of~320sccm is passed through inert gas, is passed through hydrogen with the flow of 3~5sccm, is cooled to room temperature, that is, makes to tube furnace
The graphene for having twin nuclei must be grown.
2. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
The step 1) stated further includes pre-processing before copper foil is put into tube furnace to copper foil, the preprocessing process are as follows: by copper
Foil, which is put into dilute hydrochloric acid, to be cleaned by ultrasonic, and is then transferred in acetone soln and is cleaned by ultrasonic, with height after cleaning
Pressure is dried with nitrogen.
3. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
The inert gas of the step 1) and step 6) stated is argon gas, helium or neon.
4. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
The set temperature for the step 1) tube furnace stated is 1070 DEG C.
5. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
Stating step 2 set temperature of tube furnace into step 5) is 1070 DEG C.
6. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
Stating step 2 flow of gaseous carbon sources into step 5) is 0.5sccm.
7. a kind of preparation method of the bicyclic graphene nano structure of hexagon according to claim 1, it is characterised in that: institute
The hydrogen for stating step 2 and step 4) is passed through flow as 100sccm, and the hydrogen of the step 3) and step 5) is passed through flow and is
3sccm。
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