CN105803522A - Method for continuous preparation of large monocrystal graphene - Google Patents
Method for continuous preparation of large monocrystal graphene Download PDFInfo
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- CN105803522A CN105803522A CN201610193137.2A CN201610193137A CN105803522A CN 105803522 A CN105803522 A CN 105803522A CN 201610193137 A CN201610193137 A CN 201610193137A CN 105803522 A CN105803522 A CN 105803522A
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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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- 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
- 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
Abstract
The invention provides a method for continuous preparation of large monocrystal graphene and relates to preparation methods for the large monocrystal graphene.The method is mainly characterized in that copper foil is used as a catalyst and growth substrate, two sets of normal pressure chemical vapor deposition equipment are utilized for carrying out copper foil annealing and graphene growth separately, and the large-size high-quality graphene is obtained continuously through rotating devices at the two ends.According to the method, the technical problems that graphene prepared through a CVD method is small in monocrystal size, high in price, complicated in substrate surface processing procedure, long in growth cycle and the like are solved, and continuous preparation of large monocrystal graphene samples is realized through the very simple method.
Description
Technical field
The present invention relates to a kind of method preparing large single crystal Graphene continuously.
Background technology
Since Geim in 2004 etc. utilize mechanical stripping method obtain Graphene and disclose its uniqueness physical property since, the research of Graphene is always up the focus of Condensed Matter Physics and Material Field.This bi-dimensional cellular shape structure tightly packed by monolayer carbon atom gives the excellent optics of Graphene, electricity, mechanics and thermal property.The particularly carrier mobility of its good electric conductivity and superelevation so that one of most possible material of substituted for silicon that Graphene is acknowledged as in field of electronic devices.
Ruoff in 2009 et al. finds first, utilizes chemical vapour deposition technique (CVD), using Copper Foil as substrate and catalyst, it is possible to effectively obtain high-quality single-layer graphene.This method is considered as one of approach most possibly realizing Graphene industrialization production at present.But Graphene prepared by CVD exists a very big problem, the Graphene namely synthesized mostly is polycrystalline structure, and the existence of crystal boundary can reduce mobility and the electric conductivity of Graphene largely, hinders it in the application of field of electronic devices.Therefore reduce grain boundary density or growing large-size single crystal graphene becomes the hot issue that Graphene CVD growth is studied.Current CVD growth Copper Foil used by Graphene is generally polycrystalline Copper Foil, and the quality of Graphene all can be had a great impact by the different crystal orientation of Copper Foil, defect, roughness and crystal boundary.Crystal boundary and fault location often become preferential forming core point, and on the copper crystal face of most orientations, Graphene farmland district is oriented to random distribution, and therefore the crystal boundary of polycrystalline Copper Foil and defect concentration, grain size can determine the size in Graphene farmland district to a certain extent.It should be noted that on Cu (111) face, owing to its lattice paprmeter is mated with the lattice symmetry of Graphene, under suitable growth conditions, Graphene farmland district orientation is consistent, and therefore farmland district will not produce crystal boundary when merging.Namely utilize monocrystalline Cu (111) that the growth of large single crystal Graphene can be realized.But, use monocrystalline Copper Foil can be greatly enhanced cost, be unfavorable for the industrialization process of Graphene.There is bibliographical information, by polycrystalline copper being done suitable heat treatment, it is possible to be translated into great Chou district Cu (111).Therefore, by polycrystalline Copper Foil heat treatment and CVD method growth Graphene reasonable combination, it is achieved preparing large-size monocrystal graphene continuously, practical application and industrialization for Graphene are significant.
Summary of the invention
The present invention proposes one and utilizes tumbler and Copper Foil single crystallization, it is achieved grow the method for large single crystal Graphene, device and the large single crystal Graphene thus prepared on polycrystalline Copper Foil continuously.
A kind of method preparing large single crystal Graphene continuously, centers tumbler at the dress preparing Graphene, makes the substrate of superficial growth Graphene be wound up into continuously on described tumbler, thus realizing the continuous growth of Graphene.
Preferably, described substrate is Copper Foil；Preferably, described Copper Foil is the polycrystalline Copper Foil being doped with metallic element；It is further preferred that described Copper Foil does not carry out any surface treatment.
Preferably, the described device preparing Graphene includes being arranged at the first chemical vapor depsotition equipment of annealed zone and being arranged at the second chemical vapor depsotition equipment of vitellarium, wherein the first chemical vapor depsotition equipment is for being annealed described substrate, and the second chemical vapor depsotition equipment is for substrate surface growth Graphene after annealing.
Preferably, the described device preparing Graphene includes annealed zone and vitellarium, and described tumbler includes being arranged at second runner of more than 1 of vitellarium；Preferably, the number of described second runner is 1-10.
Preferably, the described device preparing Graphene also includes the first runner of being arranged at annealed zone；Preferably, the number of described first runner is 1-10.
Preferably, described method comprises the steps: to be fixed on the first runner of annealed zone by one of them end of unannealed substrate, unannealed substrate is wrapped on the first runner of annealed zone, then another end of unannealed substrate is fixed on the second runner of vitellarium.
Preferably, described method comprises the steps:
(1), the Copper Foil as substrate is wound on the first runner in the first chemical vapor depsotition equipment in advance, and another end of Copper Foil is fixed on the second runner in the second chemical vapor depsotition equipment, pass into noble gas, then start to warm up；
(2), temperature is when rising to 700～1100 DEG C, controls driving device and slowly rotates the second runner or rotate the first runner and the second runner simultaneously, makes Copper Foil slow transit through in the first chemical vapor depsotition equipment continuously, carry out copper foil annealing；
(3) in the second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 0.5～50sccm, H2Flow is 0.2～50sccm, starts growth course；
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene；
Preferably, described method comprises the steps:
(1), being placed in the first and second chemical vapor depsotition equipments by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is more than 300sccm, then starts to warm up, and temperature-rise period continues 50～70min；
(2) when, temperature rises to 700～1100 DEG C, control driving device slowly rotate the second runner or rotate the first runner and the second runner simultaneously, making Copper Foil slow transit through in the first chemical vapor depsotition equipment continuously, Copper Foil translational speed is 0.4-40cm/min, carries out copper foil annealing；
(3), in the second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 0.5～50sccm, H2Flow is 0.2～50sccm, starts growth course；
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
Preferably, step one, heat up in two, three and four, annealing and growth course carry out all in atmospheric conditions.
A kind of large single crystal Graphene, described large single crystal Graphene is prepared by said method, and described large single crystal Graphene is of a size of centimetres (0.1cm-10cm), and the length of graphene film is below 5m, and width is below 0.5m.
A kind of device preparing large single crystal Graphene continuously, arranges tumbler in said device, makes the substrate of superficial growth Graphene be wound up into continuously on described tumbler, thus realizing the continuous growth of Graphene.
Preferably, the described device preparing large single crystal Graphene includes being arranged at the first chemical vapor depsotition equipment of annealed zone and being arranged at the second chemical vapor depsotition equipment of vitellarium, wherein the first chemical vapor depsotition equipment is for being annealed described substrate, and the second chemical vapor depsotition equipment is for substrate surface growth Graphene after annealing.
Preferably, the described device preparing large single crystal Graphene includes annealed zone and vitellarium, and described tumbler includes being arranged at second runner of more than 1 of vitellarium；Preferably, the number of described second runner is 1-10.
Preferably, the described device preparing large single crystal Graphene also includes the first runner of being arranged at annealed zone；Preferably, the number of described first runner is 1-10.Present invention Copper Foil, as catalyst and growth substrate, uses aumospheric pressure cvd method, obtains the Graphene of large-size high-quality continuously.The method that the present invention proposes, solves graphene domain size prepared by CVD method little, and electrical properties such as is substantially reduced at the technical problem, by very simple method, it is achieved that prepare high-quality large single crystal Graphene continuously.
It is an advantage of the current invention that:
1. the present invention selects Copper Foil as growth substrates, it is not necessary to substrate carries out the surface preparation of complexity, is greatly simplified growth operation, shortens growth cycle, greatly reduces preparation cost；
2. Copper Foil only need to be annealed by the present invention in chemical gas-phase deposition system, can prepare large size single crystal Cu (111), it is not necessary to other any special process；
3. the present invention proposes a kind of method for designing that can prepare Graphene continuously.
4. the invention provides a kind of method preparing large single crystal Graphene continuously, the Graphene prepared, defect is few, and quality is high, has a good application prospect in micro-nano field of electronic devices；
5. the inventive method is simple, effective, and manufacturing cycle is short, contributes to practical application and the industrialized production of Graphene.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes chemical vapour deposition technique to prepare the device schematic diagram of large single crystal Graphene continuously.
Fig. 2 is the LEED result of the large single crystal Cu (111) testing a preparation in embodiment one.
Fig. 3 is the optical picture of the graphene domain sample testing a preparation in embodiment one.
Fig. 4 is the Raman spectrogram of the single crystal graphene testing a preparation in embodiment one, it was shown that prepared sample is high quality monolayer Graphene.
Fig. 5 is the optical picture of the four inches of graphene film samples testing a preparation in embodiment one.
Fig. 6 is electron backscattered (EBSD) result of the Copper Foil substrate of embodiment two preparation.
Fig. 7 is the optical picture of graphene domain sample on the polycrystalline Copper Foil of embodiment two preparation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention being described in further details, described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions, and if Copper Foil is to buy from AlfaAesar, thickness is 25 μm or 127 μm, is directly placed in CVD system by Copper Foil and grows.
Fig. 1 is that the present invention utilizes chemical vapour deposition technique to prepare the device schematic diagram of large single crystal Graphene continuously, described device includes annealed zone and vitellarium, annealed zone can include a CVD chamber, vitellarium can also include a CVD chamber, the left end of annealed zone 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 at a distance；Or a little cavity can be connected between annealed zone and vitellarium, with the N of an atm higher2Deng the little cavity of inert gas shielding, thus preventing the Copper Foil oxidation passed through wherein.
More than one first runner is set near one end of entrance in annealed zone, in vitellarium, more than one second runner is set near one end of outlet.Size according to CVD chamber, the quantity of the first runner is 1-10, and the quantity of the second runner is 1-10.The runner of annealed zone is drivewheel or driven pulley, and the runner of vitellarium is drivewheel.When the runner of annealed zone and the runner of vitellarium are drivewheel, it is possible to be arranged as required to the relative rotation speed between two runners, thus the tension force adjusted on Copper Foil.
When preparing large single crystal Graphene continuously, one of them end needing the original Copper Foil of annealing is fixed on the first runner of annealed zone, original Copper Foil is wrapped on the first runner of annealed zone, then another end of original Copper Foil is fixed on the second runner of vitellarium.All fill protective gas with in annealed zone and vitellarium, then second runner in rotated growth district, or the runner of annealed zone and vitellarium can be made simultaneously to rotate.In the process, original Copper Foil first passes through annealed zone, and original Copper Foil becomes monocrystalline Copper Foil from polycrystalline Copper Foil；Then, monocrystalline Copper Foil, through vitellarium, goes out large single crystal Graphene in monocrystalline Copper Foil superficial growth.Under the rotation of the second runner of vitellarium, the monocrystalline Copper Foil of the good large single crystal Graphene of superficial growth is just wound on the second runner of vitellarium, it is achieved thereby that Copper Foil is from the first runner of annealed zone to the transfer of the second runner of vitellarium, and obtain the monocrystalline Copper Foil of the good large single crystal Graphene of superficial growth.
Embodiment one: a kind of method preparing large single crystal Graphene continuously
Present embodiment is to carry out in the device shown in Fig. 1, and wherein, described device respectively arranges a runner in annealed zone and vitellarium, namely includes 1 the first runner being arranged at annealed zone and 1 the second runner being arranged at vitellarium.Being previously wound around on the first runner of annealed zone by the original Copper Foil not past annealing, another end of original Copper Foil is connected on the second runner of vitellarium, and sequentially includes the following steps:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 300sccm, then starts to warm up, and temperature-rise period continues 60min；
(2) when, temperature rises to 1000 DEG C, control driving or tumbler slowly rotates two ends runner, make Copper Foil slow transit through in chemical gas-phase deposition system continuously, rotating speed (runner linear velocity, it is also equal to Copper Foil translational speed) for 4cm/min, carry out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
It should be understood that
If Copper Foil is carried out surface treatment by 1, then apply it to and there is equally possible acquisition large single crystal Graphene in the method for above-mentioned steps.
2, to using the paillon foil of other materials as substrate to grow the situation of large single crystal Graphene, this set up equally in the way of carrying out continuously growth by arranging runner.
3, driving device therein can be motor, cylinder etc..
Operating pressure in said method is normal pressure, is an atmospheric pressure or about 1 × 105Pa。
Present embodiment includes following beneficial effect:
1, present embodiment selects the metal copper foil easily obtained as catalyst and growth substrates, it is possible to the acquisition large single crystal Graphene of high-repetition-rate.
2, present embodiment is with the Copper Foil directly bought for substrate, it is not necessary to other special surfaces process, and reduce growth cost.
3, present embodiment utilizes actuating device can realize growth large single crystal Graphene continuously.
4, the large single crystal Graphene size of present embodiment growth is big, quality is high, defect is few, has extraordinary application prospect in future electronic.
Beneficial effects of the present invention is verified by tests below:
Test one: a kind of method preparing large single crystal Graphene continuously of this test is to sequentially include the following steps:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 300sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1000 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
The LEED result of the large single crystal Cu (111) of this test annealing preparation is as shown in Figure 2, it can be seen that become monocrystalline Cu (111) after the annealing of polycrystalline copper paper tinsel.The optical picture of the Graphene monocrystalline of preparation is as it is shown on figure 3, graphene domain orientation keeps consistent.As shown in Figure 4, by Raman spectrum it can be seen that Graphene has sharp 2D peak, G peak, wherein the strength ratio at 2D peak and G peak is about the halfwidth at 2.2,2D peaks and is about 39cm the Raman spectrum (optical maser wavelength is 532nm) of the Graphene of preparation-1, illustrate that prepared sample is single-layer graphene.Additionally, do not find D peak in graphite Raman spectrum, illustrating that the single crystal graphene size that we prepare is big, quality is high.
Test two: a kind of method preparing large single crystal Graphene continuously of this test is to sequentially include the following steps:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 300sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1050 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
The graphene domain size of this test preparation is big, quality is high, and orientation is consistent.
Test three: a kind of method preparing large single crystal Graphene continuously of this test is to sequentially include the following steps:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 300sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1000 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 50sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
The graphene domain size of this test preparation is big, quality is high, and orientation is consistent.
Test four: a kind of method preparing large single crystal Graphene continuously of this test is to sequentially include the following steps:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 500sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1000 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
The graphene domain size of this test preparation is big, quality is high, and orientation is consistent.
Embodiment two: the effect checking of Copper Foil doped metallic elements in a kind of method preparing large single crystal Graphene continuously of this test:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil of undoped p metallic element, pass into Ar, flow is 300sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1000 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain Graphene sample.
The Copper Foil substrate of this test preparation is polycrystalline Copper Foil, EBSD result such as Fig. 6.Copper Foil is polycrystalline, Graphene farmland orientation disorder (optical picture is Fig. 7 such as) of growth on Copper Foil.Through contrasting (optical picture is Fig. 3 such as) with the Graphene sample prepared by test one in embodiment one, in other growth conditionss (growth temperature, growth time, gas flow) identical situation, with unadulterated Copper Foil as substrate, prepared Copper Foil is polycrystalline copper, Graphene farmland orientation is mixed and disorderly, it is impossible to seamless spliced one-tenth oversized single crystal Graphene.
Embodiment three: the effect checking of oxygen in a kind of method preparing large single crystal Graphene continuously of this test:
(1), being placed in chemical vapor depsotition equipment by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is 300sccm, and the stove of annealed zone passes into H simultaneously2Gas, H2Flow is 20sccm, then starts to warm up, and temperature-rise period continues 60min；
(2), temperature is when rising to 1000 DEG C, controls tumbler and slowly rotates two ends runner, makes Copper Foil slow transit through in chemical gas-phase deposition system continuously, and rotating speed is 4cm/min, carries out copper foil annealing.
(3), in second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 5sccm, H2Flow is 20sccm, starts growth course.
(4), growth terminate after, be cooled to room temperature, namely obtain Graphene sample.
The Copper Foil substrate of this test preparation is polycrystalline Copper Foil, the Graphene farmland orientation disorder of growth on Copper Foil.Through contrasting (optical picture is Fig. 3 such as) with the Graphene sample prepared by test one in embodiment one, in other growth conditionss (growth temperature, growth time, gas flow) identical situation, anneal under oxygen-free environment, prepared Copper Foil is polycrystalline copper, Graphene farmland orientation is mixed and disorderly, it is impossible to seamless spliced one-tenth oversized single crystal Graphene.
Claims (13)
1. the method preparing large single crystal Graphene continuously, it is characterised in that center tumbler at the dress preparing Graphene, makes the substrate of superficial growth Graphene be wound up into continuously on described tumbler, thus realizing the continuous growth of Graphene.
2. method according to claim 1, it is characterised in that described substrate is Copper Foil；Preferably, described Copper Foil is the polycrystalline Copper Foil being doped with metallic element；It is further preferred that described Copper Foil does not carry out any surface treatment.
3. method according to claim 1, it is characterized in that, the described device preparing Graphene includes being arranged at the first chemical vapor depsotition equipment of annealed zone and being arranged at the second chemical vapor depsotition equipment of vitellarium, wherein the first chemical vapor depsotition equipment is for being annealed described substrate, and the second chemical vapor depsotition equipment is for substrate surface growth Graphene after annealing.
4. method according to claim 1, it is characterised in that the described device preparing Graphene includes annealed zone and vitellarium, described tumbler includes being arranged at second runner of more than 1 of vitellarium；Preferably, the number of described second runner is 1-10.
5. method according to claim 4, it is characterised in that the described device preparing Graphene also includes the first runner being arranged at annealed zone；Preferably, the number of described first runner is 1-10.
6. method according to claim 5, it is characterized in that, described method comprises the steps: to be fixed on the first runner of annealed zone by one of them end of unannealed substrate, unannealed substrate is wrapped on the first runner of annealed zone, then another end of unannealed substrate is fixed on the second runner of vitellarium.
7. method according to claim 1, it is characterised in that described method comprises the steps:
(1), the Copper Foil as substrate is wound on the first runner in the first chemical vapor depsotition equipment in advance, and another end of Copper Foil is fixed on the second runner in the second chemical vapor depsotition equipment, pass into noble gas, then start to warm up；
(2), temperature is when rising to 700～1100 DEG C, controls driving device and slowly rotates the second runner or rotate the first runner and the second runner simultaneously, makes Copper Foil slow transit through in the first chemical vapor depsotition equipment continuously, carry out copper foil annealing；
(3) in the second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 0.5～50sccm, H2Flow is 0.2～50sccm, starts growth course；
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene；
Preferably, described method comprises the steps:
(1), being placed in the first and second chemical vapor depsotition equipments by the Copper Foil not carrying out any surface treatment, pass into Ar, flow is more than 300sccm, then starts to warm up, and temperature-rise period continues 50～70min；
(2) when, temperature rises to 700～1100 DEG C, control driving device slowly rotate the second runner or rotate the first runner and the second runner simultaneously, making Copper Foil slow transit through in the first chemical vapor depsotition equipment continuously, Copper Foil translational speed is 0.4-40cm/min, carries out copper foil annealing；
(3), in the second chemical vapor depsotition equipment, pass into CH simultaneously4And H2Gas, CH4Flow is 0.5～50sccm, H2Flow is 0.2～50sccm, starts growth course；
(4), growth terminate after, be cooled to room temperature, namely obtain large single crystal Graphene.
8. method according to claim 7, it is characterised in that step one, heat up in two, three and four, annealing and growth course carry out all in atmospheric conditions.
9. a large single crystal Graphene, it is characterized in that, described large single crystal Graphene is prepared by the method described in any one of claim 1-8, and described large single crystal Graphene is of a size of centimetres (0.1cm-10cm), the length of graphene film is below 5m, and width is below 0.5m.
10. the device preparing large single crystal Graphene continuously, it is characterised in that arrange tumbler in said device, makes the substrate of superficial growth Graphene be wound up into continuously on described tumbler, thus realizing the continuous growth of Graphene.
11. device according to claim 10, it is characterized in that, the described device preparing large single crystal Graphene includes being arranged at the first chemical vapor depsotition equipment of annealed zone and being arranged at the second chemical vapor depsotition equipment of vitellarium, wherein the first chemical vapor depsotition equipment is for being annealed described substrate, and the second chemical vapor depsotition equipment is for substrate surface growth Graphene after annealing.Two chemical vapor depsotition equipments can be used in combination, it is also possible to is separately used alone.
12. device according to claim 10, it is characterised in that the described device preparing large single crystal Graphene includes annealed zone and vitellarium, described tumbler includes being arranged at second runner of more than 1 of vitellarium；Preferably, the number of described second runner is 1-10.
13. device according to claim 12, it is characterised in that the described device preparing large single crystal Graphene also includes the first runner being arranged at annealed zone；Preferably, the number of described first runner is 1-10.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702483A (en) * | 2017-03-27 | 2017-05-24 | 重庆墨希科技有限公司 | Continuous graphene growth equipment with vertically arranged high-temperature process cavity |
| CN106835260A (en) * | 2017-01-12 | 2017-06-13 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN106835068A (en) * | 2017-03-27 | 2017-06-13 | 重庆墨希科技有限公司 | The continuous growth apparatus of rolling Graphene |
| CN108441948A (en) * | 2018-04-24 | 2018-08-24 | 华中科技大学 | A kind of preparation method of the micro-nano crystal array of wafer level graphene |
| 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 |
| CN108728813A (en) * | 2017-04-25 | 2018-11-02 | 北京大学 | A kind of method and device quickly continuously preparing oversized single crystal film |
| CN109506813A (en) * | 2018-12-10 | 2019-03-22 | 中国航发四川燃气涡轮研究院 | A kind of method for annealing in thermometric crystal probe calibration process |
| CN109652858A (en) * | 2018-12-11 | 2019-04-19 | 北京大学 | A method of monocrystalline hexagonal boron nitride is prepared using the synergistic effect that layer coupling is coupled with step |
| CN110195251A (en) * | 2019-07-04 | 2019-09-03 | 北京石墨烯研究院 | Monocrystalline copper foil and preparation method thereof |
| CN111690982A (en) * | 2019-03-11 | 2020-09-22 | 北京大学 | Method for growing single crystal graphene by using single crystal copper foil with any index surface |
| CN111876703A (en) * | 2020-07-28 | 2020-11-03 | 江南大学 | Method for preparing graphene-grown single crystal copper substrate through stepping motor in vacuum |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070125493A1 (en) * | 2005-12-05 | 2007-06-07 | Jang Bor Z | Method for producing highly conductive sheet molding compound, fuel cell flow field plate, and bipolar plate |
| CN102534766A (en) * | 2012-02-28 | 2012-07-04 | 无锡第六元素高科技发展有限公司 | Device for quickly and continuously preparing large-size graphene film and application thereof |
| CN102586868A (en) * | 2012-02-06 | 2012-07-18 | 中国科学院金属研究所 | Preparation method of large-size single-crystal graphene and continuous thin film thereof |
| CN102828161A (en) * | 2012-08-21 | 2012-12-19 | 许子寒 | Graphene production method and continuous production device of graphene |
| CN102995119A (en) * | 2011-09-08 | 2013-03-27 | 中国科学院上海硅酸盐研究所 | Large-dimension hexagonal bi-layer grapheme single-crystal domain and preparation method thereof |
| CN103643288A (en) * | 2013-11-29 | 2014-03-19 | 中国科学院金属研究所 | Preparation method of high-quality large-size monocrystal graphene |
| CN104389016A (en) * | 2014-10-27 | 2015-03-04 | 中国科学院化学研究所 | Method for quickly preparing large-size single-crystal graphene |
-
2016
- 2016-03-30 CN CN201610193137.2A patent/CN105803522B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070125493A1 (en) * | 2005-12-05 | 2007-06-07 | Jang Bor Z | Method for producing highly conductive sheet molding compound, fuel cell flow field plate, and bipolar plate |
| CN102995119A (en) * | 2011-09-08 | 2013-03-27 | 中国科学院上海硅酸盐研究所 | Large-dimension hexagonal bi-layer grapheme single-crystal domain and preparation method thereof |
| CN102586868A (en) * | 2012-02-06 | 2012-07-18 | 中国科学院金属研究所 | Preparation method of large-size single-crystal graphene and continuous thin film thereof |
| CN102534766A (en) * | 2012-02-28 | 2012-07-04 | 无锡第六元素高科技发展有限公司 | Device for quickly and continuously preparing large-size graphene film and application thereof |
| CN102828161A (en) * | 2012-08-21 | 2012-12-19 | 许子寒 | Graphene production method and continuous production device of graphene |
| CN103643288A (en) * | 2013-11-29 | 2014-03-19 | 中国科学院金属研究所 | Preparation method of high-quality large-size monocrystal graphene |
| CN104389016A (en) * | 2014-10-27 | 2015-03-04 | 中国科学院化学研究所 | Method for quickly preparing large-size single-crystal graphene |
Non-Patent Citations (2)
| Title |
|---|
| THORSTEN HESJEDAL: "Continuous roll-to-roll growth of graphene films by chemical vapor deposition", 《APPLIED PHYSICS LETTERS》 * |
| ZHEN-YU JUANG ET AL.: "Graphene synthesis by chemical vapor deposition and transfer by a roll-to-roll process", 《CARBON》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835260A (en) * | 2017-01-12 | 2017-06-13 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN106835260B (en) * | 2017-01-12 | 2019-01-29 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN106702483B (en) * | 2017-03-27 | 2020-01-03 | 重庆墨希科技有限公司 | Graphene continuous growth equipment with vertically arranged high-temperature process cavity |
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| CN106702483A (en) * | 2017-03-27 | 2017-05-24 | 重庆墨希科技有限公司 | Continuous graphene growth equipment with vertically arranged high-temperature process cavity |
| CN108728813A (en) * | 2017-04-25 | 2018-11-02 | 北京大学 | A kind of method and device quickly continuously preparing oversized single crystal film |
| CN108728813B (en) * | 2017-04-25 | 2020-02-11 | 北京大学 | Method and device for rapidly and continuously preparing oversized single crystal film |
| CN108441948A (en) * | 2018-04-24 | 2018-08-24 | 华中科技大学 | A kind of preparation method of the micro-nano crystal array of wafer level graphene |
| 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 |
| CN109506813A (en) * | 2018-12-10 | 2019-03-22 | 中国航发四川燃气涡轮研究院 | A kind of method for annealing in thermometric crystal probe calibration process |
| CN109506813B (en) * | 2018-12-10 | 2020-12-29 | 中国航发四川燃气涡轮研究院 | Annealing method in calibration process of temperature measurement crystal sensor |
| CN109652858A (en) * | 2018-12-11 | 2019-04-19 | 北京大学 | A method of monocrystalline hexagonal boron nitride is prepared using the synergistic effect that layer coupling is coupled with step |
| 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 |
| CN111690982A (en) * | 2019-03-11 | 2020-09-22 | 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 |
| CN111876703A (en) * | 2020-07-28 | 2020-11-03 | 江南大学 | Method for preparing graphene-grown single crystal copper substrate through stepping motor in vacuum |
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