CN105803522B - A kind of continuous method for preparing large single crystal graphene - Google Patents
A kind of continuous method for preparing large single crystal graphene Download PDFInfo
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- CN105803522B CN105803522B CN201610193137.2A CN201610193137A CN105803522B CN 105803522 B CN105803522 B CN 105803522B CN 201610193137 A CN201610193137 A CN 201610193137A CN 105803522 B CN105803522 B CN 105803522B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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Abstract
The invention provides a kind of continuous method for preparing large single crystal graphene, it is related to the preparation method of large single crystal graphene.It is mainly characterized by, by the use of copper foil as catalyst and growth substrate, separately carrying out copper foil annealing and graphene growth using two aumospheric pressure cvd equipment, passing through the graphene of the tumbler at both ends, continuously acquisition large-size high-quality.Method proposed by the present invention, solve small graphene monocrystalline size prepared by CVD method, expensive, substrate surface treatment process complexity and the technical problem such as growth cycle length, by very simple method, realize and continuously prepare large single crystal graphene sample.
Description
Technical field
The present invention relates to a kind of continuous method for preparing large single crystal graphene.
Background technology
Since Geim in 2004 etc. obtains graphene using mechanical stripping method and discloses its unique physical property,
Research to graphene is always the focus of Condensed Matter Physics and Material Field.It is this to be formed by single layer of carbon atom is tightly packed
Bi-dimensional cellular shape structure assigns graphene excellent optics, electricity, mechanics and thermal property.Particularly its good electric conductivity
And the carrier mobility of superelevation so that the most possible substituted for silicon that graphene is acknowledged as in field of electronic devices
One of material.
Ruoff in 2009 et al. is had found first, and using chemical vapour deposition technique (CVD), substrate and catalysis are used as using copper foil
Agent, the single-layer graphene of high quality can be effectively obtained.This method is considered as most possibly to realize that graphene produces at present
One of approach of industry metaplasia production.But graphene prepared by CVD has the problem of one very big, that is, the graphene synthesized is mostly more
Crystal structure, and the presence of crystal boundary can largely reduce the mobility and electric conductivity of graphene, hinder it in electronic device
The application in field.Therefore reducing grain boundary density or growing large-size single crystal graphene turns into the one of the research of graphene CVD growth
Individual hot issue.Copper foil used in current CVD growth graphene is usually polycrystalline copper foil, the different crystal orientation of copper foil, is lacked
Fall into, roughness and crystal boundary can have a great impact to the quality of graphene.Crystal boundary and fault location often turn into preferential shape
Epipole, on the copper crystal face of majority orientation, graphene farmland area is oriented to random distribution, therefore the crystal boundary and defect of polycrystalline copper foil
Density, grain size can determine the size in graphene farmland area to a certain extent.It is worth noting that on Cu (111) face, by
Matched in its lattice constant with the lattice symmetry of graphene, under suitable growth conditions, graphene farmland area orientation is consistent, because
This farmland area will not produce crystal boundary when merging.The growth of large single crystal graphene can be achieved using monocrystalline Cu (111).However, make
Cost can be greatly enhanced with monocrystalline copper foil, is unfavorable for the industrialization process of graphene.There is document report, by being done to polycrystalline copper
Suitable heat treatment, can be translated into great Chou areas Cu (111).Therefore, the heat treatment of polycrystalline copper foil is grown into stone with CVD method
Black alkene reasonable combination, realizes continuous preparation large-size monocrystal graphene, and practical application and industrialization for graphene have weight
Want meaning.
The content of the invention
The present invention proposes that one kind utilizes tumbler and copper foil single crystallization, realizes and large single crystal is continuously grown on polycrystalline copper foil
The method, apparatus of graphene and the large single crystal graphene thus prepared.
A kind of continuous method for preparing large single crystal graphene, centers tumbler in the dress for preparing graphene, makes table
The substrate that face grown graphene is continuously wound up on the tumbler, so as to realize the continuous growth of graphene.
Preferably, the substrate is copper foil；Preferably, the copper foil is the polycrystalline copper foil for being doped with metallic element；
It is further preferred that the copper foil is without any surface treatment.
Preferably, the device for preparing graphene include be arranged at annealed zone the first chemical vapor depsotition equipment and
The second chemical vapor depsotition equipment of vitellarium is arranged at, wherein the first chemical vapor depsotition equipment is used to carry out the substrate
Annealing, the second chemical vapor depsotition equipment are used for substrate surface growth graphene after annealing.
Preferably, the device for preparing graphene includes annealed zone and vitellarium, and the tumbler includes setting
Second runner of more than 1 in vitellarium；Preferably, the number of second runner is 1-10.
Preferably, the device for preparing graphene also includes the first runner for being arranged at annealed zone；Preferably, institute
The number for stating the first runner is 1-10.
Preferably, methods described comprises the following steps：One of end of unannealed substrate is fixed on annealing
On first runner in area, unannealed substrate is wrapped on the first runner of annealed zone, then by the another of unannealed substrate
One end is fixed on the second runner of vitellarium.
Preferably, methods described comprises the following steps：
(1), it is wound in as the copper foil of substrate in advance on the first runner in the first chemical vapor depsotition equipment, and
Another end of copper foil is fixed on the second runner in the second chemical vapor depsotition equipment, is passed through inert gas, then
Start to warm up；
(2) when, temperature rises to 700~1100 DEG C, control drive device slowly rotates the second runner or rotates first simultaneously
Runner and the second runner, make copper foil continuously be slow transitted through in the first chemical vapor depsotition equipment, carry out copper foil annealing；
(3) while in the second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 0.5~50sccm,
H2Flow is 0.2~50sccm, starts growth course；
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene；
Preferably, methods described comprises the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in the first and second chemical vapor depsotition equipments, is passed through
Ar, flow are more than 300sccm, are then started to warm up, temperature-rise period continues 50~70min；
(2) when, temperature rises to 700~1100 DEG C, control drive device slowly rotates the second runner or rotates first simultaneously
Runner and the second runner, make copper foil continuously be slow transitted through in the first chemical vapor depsotition equipment, and copper foil translational speed is 0.4-
40cm/min, carry out copper foil annealing；
(3) while in the second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 0.5~50sccm,
H2Flow is 0.2~50sccm, starts growth course；
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
Preferably, Step 1: being heated up in two, three and four, annealing and growth course are carried out in atmospheric conditions.
A kind of large single crystal graphene, the large single crystal graphene are the large single crystal graphenes as prepared by the above method
Size be centimetres (0.1cm-10cm), the length of graphene film is below 5m, and width is below 0.5m.
A kind of continuous device for preparing large single crystal graphene, sets tumbler, makes superficial growth in said device
The substrate of graphene is continuously wound up on the tumbler, so as to realize the continuous growth of graphene.
Preferably, the device for preparing large single crystal graphene includes being arranged at the first chemical vapor deposition of annealed zone
Equipment and the second chemical vapor depsotition equipment for being arranged at vitellarium, wherein the first chemical vapor depsotition equipment is used for the base
Bottom is annealed, and the second chemical vapor depsotition equipment is used for substrate surface growth graphene after annealing.
Preferably, the device for preparing large single crystal graphene includes annealed zone and vitellarium, the tumbler bag
Include and be arranged at second runner of more than 1 of vitellarium；Preferably, the number of second runner is 1-10.
Preferably, the device for preparing large single crystal graphene also includes the first runner for being arranged at annealed zone；It is preferred that
, the number of first runner is 1-10.The present invention uses normal pressure chemical by the use of copper foil as catalyst and growth substrate
Vapour deposition process, the continuous graphene for obtaining large-size high-quality.Method proposed by the present invention, solves CVD method preparation
Graphene domain size is small, the technical problems such as electrical properties substantially reduce, and by very simple method, realizes continuous preparation
Go out the large single crystal graphene of high quality.
The advantage of the invention is that：
1. the present invention is from copper foil as growth substrates, it is not necessary to complicated surface preparation is carried out to substrate, it is significantly simple
The long process of metaplasia, shorten growth cycle, greatly reduce preparation cost；
2. the present invention only need to anneal copper foil in chemical gas-phase deposition system, you can prepare large size single crystal Cu
(111), it is not necessary to other any special processing；
3. the present invention proposes a kind of design method that can continuously prepare graphene.
4. the invention provides a kind of continuous method for preparing large single crystal graphene, the graphene prepared, defect is few, matter
Amount is high, is had a good application prospect in micro-nano field of electronic devices；
5. the inventive method is simple, effective, short preparation period, contribute to the practical application and industrialized production of graphene.
Brief description of the drawings
Fig. 1 is the schematic device that the present invention continuously prepares large single crystal graphene using chemical vapour deposition technique.
Fig. 2 is the LEED results of large single crystal Cu (111) prepared by experiment one in embodiment one.
Fig. 3 is the optical picture of graphene domain sample prepared by experiment one in embodiment one.
Fig. 4 is the Raman spectrogram of single crystal graphene prepared by experiment one in embodiment one, shows that prepared sample is
High quality monolayer graphene.
Fig. 5 is the optical picture of four inches of graphene film sample prepared by experiment one in embodiment one.
Fig. 6 is electron backscattered (EBSD) result of copper foil substrate prepared by embodiment two.
Fig. 7 is the optical picture of graphene domain sample on the polycrystalline copper foil of the preparation of embodiment two.
Embodiment
The present invention is described in further details with reference to specific embodiment, methods described is normal unless otherwise instructed
Rule method.The raw material can obtain from open commercial sources unless otherwise instructed, as copper foil be from Alfa Aesar purchases,
Thickness is 25 μm or 127 μm, and copper foil is directly placed into CVD system and grown.
Fig. 1 continuously prepares the schematic device of large single crystal graphene, the dress for the present invention using chemical vapour deposition technique
Put including annealed zone and vitellarium, annealed zone can include a CVD chamber, and vitellarium can also include a CVD chamber, move back
The left end of flame range is defined as arrival end, and the right-hand member of vitellarium is defined as the port of export.Annealed zone and vitellarium can be separated by one section away from
From；Or a small cavity can be connected between annealed zone and vitellarium, with the N of an atm higher2Deng inert gas
Small cavity is protected, so as to prevent the copper foil passed through wherein from aoxidizing.
More than one first runner is set close to one end of entrance in annealed zone, set in vitellarium close to one end of outlet
Put more than one second runner.According to the size of CVD chamber, the quantity of the first runner is 1-10, the quantity of the second runner
For 1-10.The runner of annealed zone is driving wheel or driven pulley, and the runner of vitellarium is driving wheel.When annealed zone runner and
When the runner of vitellarium is driving wheel, the relative rotation speed that can be arranged as required between two runners, so as to adjust copper foil
On tension force.
When continuously large single crystal graphene is prepared, it would be desirable to which one of end of the original copper foil of annealing is fixed on
On first runner of annealed zone, original copper foil is wrapped on the first runner of annealed zone, then by original copper foil another
End is fixed on the second runner of vitellarium.Protective gas is filled with annealed zone and vitellarium, then rotated growth area
The second runner, or the runner of annealed zone and vitellarium can be made while rotated.In the process, original copper foil, which first passes through, moves back
Flame range, original copper foil become monocrystalline copper foil from polycrystalline copper foil；Then, monocrystalline copper foil is given birth to by vitellarium in monocrystalline copper foil surface
Grow large single crystal graphene.Under the rotation of the second runner of vitellarium, the monocrystalline copper foil of the good large single crystal graphene of superficial growth
Just it is wound on the second runner of vitellarium, it is achieved thereby that copper foil is from the first runner of annealed zone to the second runner of vitellarium
Transfer, and obtained the monocrystalline copper foil of the good large single crystal graphene of superficial growth.
Embodiment one：A kind of continuous method for preparing large single crystal graphene
Present embodiment is carried out in the device shown in Fig. 1, wherein, described device is respectively set in annealed zone and vitellarium
A runner is put, i.e., including 1 the first runner for being arranged at annealed zone and 1 the second runner for being arranged at vitellarium.To not have
It is previously wound around by the original copper foil of annealing on the first runner of annealed zone, another end of original copper foil is connected to vitellarium
The second runner on, and carry out according to the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control driving or tumbler slowly rotate both ends runner, copper foil is continuously existed
Slow transitted through in chemical gas-phase deposition system, rotating speed (runner linear velocity, being also equal to copper foil translational speed) is 4cm/min, is carried out
Copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
It should be noted that：
If the 1, be surface-treated to copper foil, applying it in the method with above-mentioned steps can equally obtain
Large single crystal graphene.
2nd, it is this by setting runner to growing the situation of large single crystal graphene using the paillon foil of other materials as substrate
Equally set up in a manner of continuously being grown.
3rd, drive device therein can be motor, cylinder etc..
Operating pressure in the above method is normal pressure, as an atmospheric pressure or about 1 × 105Pa。
Present embodiment includes following beneficial effect：
1st, present embodiment selects the metal copper foil easily obtained as catalyst and growth substrates, can obtaining with high-repetition-rate
Obtain large single crystal graphene.
2nd, present embodiment is using the copper foil directly bought as substrate, it is not necessary to the processing of other special surfaces, reduces growth
Cost.
3rd, present embodiment can realize continuous growth large single crystal graphene using transmission device.
4th, the large single crystal graphene size of present embodiment growth is big, quality is high, defect is few, has in future electronic
Extraordinary application prospect.
Beneficial effects of the present invention are verified by tests below：
Experiment one：A kind of continuous method for preparing large single crystal graphene of this experiment is to carry out according to the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
Large single crystal Cu (111) prepared by this experiment annealing LEED results are as shown in Figure 2, it can be seen that polycrystalline copper paper tinsel is annealed
After become monocrystalline Cu (111).The optical picture of the graphene monocrystalline of preparation is as shown in figure 3, graphene domain orientation is consistent.
The Raman spectrum (optical maser wavelength 532nm) of the graphene of preparation is as shown in figure 4, by Raman spectrum, graphene has
Sharp 2D peaks, G peaks, the wherein intensity at 2D peaks and G peaks ratio is about that the halfwidth at 2.2,2D peaks is about 39cm-1, prepared by explanation
Sample be single-layer graphene.In addition, without D peaks are found in graphite Raman spectrum, illustrate the single crystal graphene that we prepare
Size is big, and quality is high.
Experiment two：A kind of continuous method for preparing large single crystal graphene of this experiment is to carry out according to the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1050 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
This experiment prepare graphene domain size is big, quality is high, orientation is consistent.
Experiment three：A kind of continuous method for preparing large single crystal graphene of this experiment is to carry out according to the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 50sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
This experiment prepare graphene domain size is big, quality is high, orientation is consistent.
Experiment four：A kind of continuous method for preparing large single crystal graphene of this experiment is to carry out according to the following steps：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
500sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
This experiment prepare graphene domain size is big, quality is high, orientation is consistent.
Embodiment two：Copper foil doped metallic elements in a kind of continuous method for preparing large single crystal graphene of this experiment
Effect checking：
(1), the copper foil undoped with metallic element is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, then start to warm up, temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains graphene sample.
Copper foil substrate prepared by this experiment is polycrystalline copper foil, EBSD results such as Fig. 6.Copper foil is polycrystalline, is grown on copper foil
Graphene farmland orientation disorder (optical picture such as Fig. 7).By being contrasted with the graphene sample prepared by experiment one in embodiment one
(optical picture such as Fig. 3), in the case where other growth conditions (growth temperature, growth time, gas flow) are identical, with not
The copper foil of doping is as substrate, and prepared copper foil is polycrystalline copper, and graphene farmland orientation is mixed and disorderly, can not be seamless spliced into super large list
Brilliant graphene.
Embodiment three：The effect checking of oxygen in a kind of continuous method for preparing large single crystal graphene of this experiment：
(1), the copper foil for not carrying out any surface treatment is placed in chemical vapor depsotition equipment, is passed through Ar, flow is
300sccm, the stove of annealed zone are passed through H simultaneously2Gas, H2Flow is 20sccm, is then started to warm up, and temperature-rise period is lasting
60min；
(2) when, temperature rises to 1000 DEG C, control tumbler slowly rotates both ends runner, makes copper foil continuously in chemical gas
Slow transitted through in phase depositing system, rotating speed 4cm/min, carry out copper foil annealing.
(3) while in second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 5sccm, H2Stream
Measure as 20sccm, beginning growth course.
(4) after, growth terminates, room temperature is cooled to, that is, obtains graphene sample.
Copper foil substrate prepared by this experiment is polycrystalline copper foil, the graphene farmland orientation disorder grown on copper foil.By with reality
Apply in mode one the graphene sample contrast (optical picture such as Fig. 3) prepared by experiment one, other growth conditions (growth temperature,
Growth time, gas flow) it is identical in the case of, annealed under oxygen-free environment, prepared copper foil is polycrystalline copper, graphite
Alkene farmland orientation is mixed and disorderly, can not be seamless spliced into oversized single crystal graphene.
Claims (7)
- A kind of 1. continuous method for preparing large single crystal graphene, it is characterised in that center rotation in the dress for preparing graphene Device, the substrate of superficial growth graphene is set continuously to be wound up on the tumbler, so as to realize the continuous life of graphene It is long；The device for preparing graphene includes being arranged at the first chemical vapor depsotition equipment of annealed zone and is arranged at vitellarium The second chemical vapor depsotition equipment, wherein the first chemical vapor depsotition equipment be used for the substrate is annealed, second change Learn the substrate surface that vapor deposition apparatus is used for after annealing and grow graphene；The tumbler includes the second runner for being arranged at more than 1 of vitellarium, and the device for preparing graphene also wraps Include the first runner for being arranged at annealed zone；Methods described comprises the following steps：(1), it is wound in as the copper foil of substrate in advance on the first runner in the first chemical vapor depsotition equipment, and by copper Another end of paper tinsel is fixed on the second runner in the second chemical vapor depsotition equipment, is passed through inert gas, is then started Heating；(2) when, temperature rises to 700~1100 DEG C, control drive device slowly rotates the second runner or rotates the first runner simultaneously With the second runner, copper foil is continuously slow transitted through in the first chemical vapor depsotition equipment, carry out copper foil annealing；(3) while in the second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 0.5~50sccm, H2Flow For 0.2~50sccm, start growth course；(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
- 2. according to the method for claim 1, it is characterised in that the copper foil is the polycrystalline copper foil for being doped with metallic element.
- 3. according to the method for claim 1, it is characterised in that the copper foil is without any surface treatment.
- 4. according to the method for claim 1, it is characterised in that the number of second runner is 1-10.
- 5. according to the method for claim 1, it is characterised in that the number of first runner is 1-10.
- 6. according to the method for claim 1, it is characterised in thatMethods described comprises the following steps：(1), the copper foil for not carrying out any surface treatment is placed in the first and second chemical vapor depsotition equipments, is passed through Ar, is flowed Measure as more than 300sccm, then start to warm up, temperature-rise period continues 50~70min；(2) when, temperature rises to 700~1100 DEG C, control drive device slowly rotates the second runner or rotates the first runner simultaneously With the second runner, copper foil is set continuously to be slow transitted through in the first chemical vapor depsotition equipment, copper foil translational speed is 0.4-40cm/ Min, carry out copper foil annealing；(3) while in the second chemical vapor depsotition equipment it is passed through CH4And H2Gas, CH4Flow is 0.5~50sccm, H2Stream Measure as 0.2~50sccm, beginning growth course；(4) after, growth terminates, room temperature is cooled to, that is, obtains large single crystal graphene.
- 7. according to the method for claim 6, it is characterised in that Step 1: heating up, annealing and growing in two, three and four Cheng Jun is carried out in atmospheric conditions.
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| CN108728813B (en) * | 2017-04-25 | 2020-02-11 | 北京大学 | Method and device for rapidly and continuously preparing oversized single crystal film |
| CN108441948B (en) * | 2018-04-24 | 2020-01-10 | 华中科技大学 | Preparation method of wafer-level graphene micro-nano single crystal array |
| CN108441951A (en) * | 2018-04-28 | 2018-08-24 | 华中科技大学 | A kind of method of quick preparation large-size monocrystal graphene |
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| CN109652858B (en) * | 2018-12-11 | 2020-09-08 | 北京大学 | Method for preparing monocrystal hexagonal boron nitride by utilizing synergistic effect of interlayer coupling and step coupling |
| CN111690982B (en) * | 2019-03-11 | 2021-04-30 | 北京大学 | Method for growing single crystal graphene by using single crystal copper foil with any index surface |
| CN110195251A (en) * | 2019-07-04 | 2019-09-03 | 北京石墨烯研究院 | Monocrystalline copper foil and preparation method thereof |
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