CN103194795A - Method for low-cost preparation of large-size monocrystal graphene - Google Patents
Method for low-cost preparation of large-size monocrystal graphene Download PDFInfo
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- CN103194795A CN103194795A CN2013101477687A CN201310147768A CN103194795A CN 103194795 A CN103194795 A CN 103194795A CN 2013101477687 A CN2013101477687 A CN 2013101477687A CN 201310147768 A CN201310147768 A CN 201310147768A CN 103194795 A CN103194795 A CN 103194795A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000001704 evaporation Methods 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 239000010445 mica Substances 0.000 claims abstract description 17
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims description 113
- 230000008020 evaporation Effects 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 27
- 238000007669 thermal treatment Methods 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- 238000005566 electron beam evaporation Methods 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001883 metal evaporation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract 3
- 239000010409 thin film Substances 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- 229910002804 graphite Inorganic materials 0.000 description 23
- 239000010439 graphite Substances 0.000 description 23
- -1 graphite alkene Chemical class 0.000 description 23
- 230000002950 deficient Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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Abstract
The invention discloses a method for low-cost preparation of large-size monocrystal graphene, relates to a preparation method of monocrystal graphene, and is used for solving the technical problems that in the chemical vapor deposition (CVD) method for preparing the large-size monocrystal graphene material, the common monocrystal substrate surface treatment process is complex, and the monocrystal substrate is difficult to reuse and high in cost. The method disclosed by the invention comprises the following steps of: I, evaporating a monocrystal metal thin film on a monocrystal mica substrate; II, placing the monocrystal metal thin film obtained from the step I into chemical vapor deposition equipment, vacuumizing and filling H2 and Ar, increasing temperature and implementing heat treatment; III, continuing to fill a CH4 gas, and depositing; and IV, closing a heating power supply, stopping filling the CH4 gas, rapidly cooling to room temperature by taking Ar and H2 as protective gases, and promoting uniform growth of high-quality monocrystal graphene on the surface of the monocrystal metal substrate. The monocrystal graphene prepared by the invention is large in size, high in quality and few in defect; and the method disclosed by the invention is applicable to monocrystal graphene material manufacturing field.
Description
Technical field
The present invention relates to prepare the method for single crystal graphite alkene.
Background technology
Graphene (graphene) is the bi-dimensional cellular shape crystalline network by the tightly packed one-tenth of monolayer carbon atom, is the elementary cell that constitutes other carbon nanomaterials.Because unique two-dirnentional structure feature and splendid crystallography quality, the current carrier of Graphene shows the behavior that is similar to photon.In addition, Graphene also has characteristics such as excellent mechanics, electricity, calorifics, optics, is expected in the acquisition widespread use of fields such as nano electron device, transparent conductive film, matrix material, catalytic material, field emmision material, electrode of solar battery, photoelectric commutator.
At present, preparation method of graphene has a lot, and the most frequently used method has mechanically peel method, chemical stripping method, SiC epitaxial growth method, chemical vapor deposition (CVD) method etc.Wherein, though the Graphene quality height that the mechanically peel method obtains, output is extremely low, efficient is low, size little (micron dimension).The chemical stripping method is owing to exist strong oxidising process, causes the Graphene defective prepared extremely many, and is second-rate and size is less.SiC epitaxial growth method efficient is low, and controllability is relatively poor, and cost Graphene higher and that obtain is difficult to shift.To recently seeing, the Graphene quality that the CVD method has simply, operates easily, prepares is higher, size big (centimetre magnitude) and transfer to the first-class advantage of other substrates easily and get most of the attention.
Yet the large size Graphene that present CVD method is prepared is most to be polycrystalline graphite alkene, exists a large amount of crystal boundaries greatly to limit mobility and the conductivity of Graphene, and mobility is generally on the low side, usually between 100～1000cm
2V
-1s
-1Therefore, in order to weaken the influence of crystal boundary, the normal single crystal substrates that adopts is (as Al at present
2O
3(0001), MgO (111) etc.) goes up the method that prepare single crystal graphite alkene behind the deposition single-crystal metal film, quality and the electric property of raising Graphene.But present employed single crystal substrates is as Al
2O
3(0001), problem such as MgO (111) etc. exists the surface treatment procedure complexity, be difficult to recycling, and is expensive has limited the mass preparation of large size single crystal grapheme material and the practical application in microelectronic device.For this reason, be necessary to further investigate in this regard, the breakthrough of this direction is significant to practical application and the suitability for industrialized production of Graphene.
Summary of the invention
The present invention will solve the CVD method to prepare single crystal substrates surface treatment procedure complexity commonly used in the large size single crystal grapheme material, is difficult to recycling and expensive technical problem, thereby provides a kind of low cost to prepare the method for large size single crystal Graphene.
The method that a kind of low cost of the present invention prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metal, is 1 * 10 at high vacuum environment
-3～1 * 10
-4Under the Pa, evaporation single-crystal metal film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02～0.20nm/s, and base reservoir temperature is 450～650 ℃, and evaporation single-crystal metal film thickness is 500～1000nm;
Two, the single-crystal metal film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 850～1000 ℃, heat treatment time is 30～120min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 0.5～10sccm, regulates H
2Flow is 10～50sccm, and the Ar flow is 800～1000sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5～30min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single-crystal metal substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The present invention includes following beneficial effect:
1, the present invention selects for use cheap monocrystalline mica (001) as substrate, at its surperficial evaporation single-crystal metal film, by regulation and control, optimization processing parameter, and then realizes on the single-crystal metal film that the low cost of large size single crystal grapheme material prepares.
2, the present invention, handles by simple mechanically peel method as substrate with monocrystalline mica (001), utilizes splitting between the monocrystalline mica splittings, can obtain brand-new and even curface; Not only saved the complex surfaces treatment process, and after the preparation of finishing Graphene and shifting, this substrate can after handling, the mechanically peel method be reused again.Truly realized the low cost preparation of large size single crystal grapheme material.
3, the inventive method simple, effectively, help practical application and the suitability for industrialized production of large size single crystal grapheme material, and the Graphene size of preparing is big, the quality height has a good application prospect in fields such as micro-nano electron device, photoelectric commutator, transparent conductive films.
Description of drawings
Fig. 1 transfers to SiO for the single crystal graphite alkene of test one preparation
2The optical microscope photograph of/Si substrate;
Fig. 2 is the Raman spectrum of the single crystal graphite alkene of test one preparation;
The FET device picture that Fig. 3 makes for the single crystal graphite alkene of test one preparation;
Fig. 4 is the single crystal graphite alkene of the test one preparation relation of field-effect-transistor resistor and carrier density at room temperature;
Fig. 5 is the single crystal graphite alkene of the test one preparation relation of field-effect transistor carrier mobility and charged impurity concentration at room temperature.
Embodiment
Embodiment one: the method that a kind of low cost of present embodiment prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metal, is 1 * 10 at high vacuum environment
-3～1 * 10
-4Under the Pa, evaporation single-crystal metal film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02～0.20nm/s, and base reservoir temperature is 450～650 ℃, and evaporation single-crystal metal film thickness is 500～1000nm;
Two, the single-crystal metal film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 850～1000 ℃, heat treatment time is 30～120min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 0.5～10sccm, regulates H
2Flow is 10～50sccm, and the Ar flow is 800～1000sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5～30min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 05～10 ℃/s, evenly grows the high quality single crystal Graphene at the single-crystal metal substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
Present embodiment comprises following beneficial effect:
1, present embodiment selects for use cheap monocrystalline mica (001) as substrate, at its surperficial evaporation single-crystal metal film, by regulation and control, optimization processing parameter, and then realizes on the single-crystal metal film that the low cost of large size single crystal grapheme material prepares.
2, present embodiment, is handled by simple mechanically peel method as substrate with monocrystalline mica (001), utilizes splitting between the monocrystalline mica splittings, can obtain brand-new and even curface.Not only saved the complex surfaces treatment process, and after the preparation of finishing Graphene and shifting, this substrate can after handling, the mechanically peel method be reused again.Truly realized the low cost preparation of large size single crystal grapheme material.
3, the present embodiment method simple, effectively, help practical application and the suitability for industrialized production of large size single crystal grapheme material, and the Graphene size of preparing is big, the quality height has a good application prospect in fields such as micro-nano electron device, photoelectric commutator, transparent conductive films.
Embodiment two: what present embodiment and embodiment one were different is: metal evaporation sources is copper, nickel or cobalt in the step 1.Other is identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is: evaporation speed is 0.02nm/s in the step 1.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is: base reservoir temperature is 450 ℃ in the step 1.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different with one of embodiment one to four is: evaporation single-crystal metal film thickness is 800nm in the step 1.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different with one of embodiment one to five is: being warming up to thermal treatment temp in the step 2 is 1000 ℃.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: heat treatment time is 30min in the step 2.Other is identical with one of embodiment one to six.
By following verification experimental verification beneficial effect of the present invention:
Test one: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic copper, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation single crystal Cu film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation single crystal Cu film thickness is 800nm;
Two, the single crystal Cu film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 1sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single crystal Cu substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene of this test preparation is transferred to SiO
2The optical microscope photograph of/Si substrate as shown in Figure 1, the Raman spectrum (optical maser wavelength is 488nm) of the single crystal graphite alkene of this test preparation as shown in Figure 2, wherein, Graphene uniform surface, the size prepared are big, by G in the Raman spectrum, and the strong ratio in the position at 2D peak and relative peak, the Graphene that preparation can be described all is individual layer single crystal graphite alkene substantially, and do not have the D peak to occur, illustrated that the single crystal graphite alkene quality of preparation is high, defective is few.Single-layer graphene proportion (individual layer rate) is 95% in the Graphene of preparation.
The FET device picture that the single crystal graphite alkene of this test preparation is made as shown in Figure 3, the single crystal graphite alkene of this test preparation at room temperature field-effect-transistor resistor and carrier density relation as shown in Figure 4, the single crystal graphite alkene of this test preparation at room temperature field-effect transistor carrier mobility and charged impurity concentration relation as shown in Figure 5, wherein, be 1 * 10 in charged impurity concentration
12Cm
-2The time, the carrier mobility of single crystal graphite alkene is 4500cm
2V
-1s
-1, illustrate that single crystal graphite alkene has excellent electric property.
Test two: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic copper, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation single crystal Cu film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation single crystal Cu film thickness is 800nm;
Two, the single crystal Cu film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 5sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single crystal Cu substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, the quality height, and defective is few, and the individual layer rate is 75%.
Test three: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic copper, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation single crystal Cu film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation single crystal Cu film thickness is 800nm;
Two, the single crystal Cu film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 10sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single crystal Cu substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, and quality is slightly poor, and defective is many, and the individual layer rate is 35%.
Test four: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic copper, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation single crystal Cu film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation single crystal Cu film thickness is 800nm;
Two, the single crystal Cu film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 1sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 15min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single crystal Cu substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, the quality height, and defective is few, and the individual layer rate is 70%.
Test five: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic copper, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation single crystal Cu film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation single crystal Cu film thickness is 800nm;
Two, the single crystal Cu film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 1sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 30min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single crystal Cu substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, and quality is slightly poor, and defective is slightly many, and the individual layer rate is 49%.
Test six: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic nickel, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation monocrystalline nickel film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation monocrystalline nickel film thickness is 800nm;
Two, the monocrystalline nickel film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 1sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 15min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the monocrystal nickel-base basal surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, the quality height, and defective is few, and the individual layer rate is 76%.
Test seven: the method that a kind of low cost of this test prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metallic nickel, is 1 * 10 at high vacuum environment
-3Under the Pa, evaporation monocrystalline nickel film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02nm/s, and base reservoir temperature is 450 ℃, and evaporation monocrystalline nickel film thickness is 800nm;
Two, the monocrystalline nickel film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 1000 ℃, heat treatment time is 30min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 5sccm, regulates H
2Flow is 20sccm, and the Ar flow is 979sccm, and operating pressure is 1 * 10
5Pa, depositing time are 15min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the monocrystal nickel-base basal surface, namely finishes low-cost preparation large size single crystal Graphene.
The single crystal graphite alkene size of this test preparation is big, the quality height, and defective is few, and the individual layer rate is 66%.
Claims (7)
1. low-cost method that prepare the large size single crystal Graphene is characterized in that the method that low cost prepares the large size single crystal Graphene is to carry out according to the following steps:
One, adopting the electron beam evaporation plating method, is evaporation source with the metal, is 1 * 10 at high vacuum environment
-3～1 * 10
-4Under the Pa, evaporation single-crystal metal film on the monocrystalline mica substrate; Wherein, evaporation speed is 0.02～0.20nm/s, and base reservoir temperature is 450～650 ℃, and evaporation single-crystal metal film thickness is 500～1000nm;
Two, the single-crystal metal film that step 1 is obtained is put into chemical vapor depsotition equipment, is evacuated to 3Pa, feeds H
2, Ar, H
2Flow is 50sccm, and the Ar flow is 100sccm, and operating pressure is 1 * 10
5Pa, being warming up to thermal treatment temp then is 850～1000 ℃, heat treatment time is 30～120min;
Three, after thermal treatment finishes, be warming up to 1000 ℃, continue to feed CH
4Gas, CH
4Flow is 0.5～10sccm, regulates H
2Flow is 10～50sccm, and the Ar flow is 800～1000sccm, and operating pressure is 1 * 10
5Pa, depositing time are 5～30min;
Four, after deposition finishes, close heating power supply, stop to feed CH
4Gas is with Ar and H
2Be shielding gas, be cooled fast to room temperature, the speed of cooling is 10 ℃/s, evenly grows the high quality single crystal Graphene at the single-crystal metal substrate surface, namely finishes low-cost preparation large size single crystal Graphene.
2. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, it is characterized in that metal evaporation sources is copper, nickel or cobalt in the step 1.
3. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, it is characterized in that evaporation speed is 0.02nm/s in the step 1.
4. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, it is characterized in that base reservoir temperature is 450 ℃ in the step 1.
5. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, it is characterized in that evaporation single-crystal metal film thickness is 800nm in the step 1.
6. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, and it is characterized in that being warming up in the step 2 thermal treatment temp is 1000 ℃.
7. a kind of low cost according to claim 1 prepares the method for large size single crystal Graphene, it is characterized in that heat treatment time is 30min in the step 2.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674343A (en) * | 2015-02-06 | 2015-06-03 | 北京大学 | Large single crystal graphene and preparation method thereof |
| CN105112998A (en) * | 2015-09-07 | 2015-12-02 | 北京大学 | Oxide-substrate-assisted method for quickly preparing large-size single-crystal graphene |
| CN105483824A (en) * | 2016-01-11 | 2016-04-13 | 信阳师范学院 | Method for preparing monocrystal double-layer graphene |
| CN105734525A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Method for preparing graphene thin film through chemical vapor deposition |
| WO2017041401A1 (en) * | 2015-09-07 | 2017-03-16 | Peking University | Rapid growth of large single-crystal graphene assisted by adjacent oxide substrate |
| CN108193276A (en) * | 2017-12-28 | 2018-06-22 | 中国科学院半导体研究所 | The method for preparing the single-orientated hexagonal boron nitride two-dimensional atomic crystal of large area |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080107876A1 (en) * | 2006-03-27 | 2008-05-08 | Postech Foundation | Zinc Oxide Microstructures and a Method of Preparing the Same |
| CN101462717A (en) * | 2007-12-17 | 2009-06-24 | 三星电子株式会社 | Single crystalline graphene sheet and process of preparing the same |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| JP2011178644A (en) * | 2010-03-04 | 2011-09-15 | National Institute For Materials Science | Epitaxial growing method of graphene film |
| CN102296361A (en) * | 2011-09-05 | 2011-12-28 | 电子科技大学 | Preparation method of single crystal graphene |
| 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 |
| JP2012232860A (en) * | 2011-04-28 | 2012-11-29 | Fuji Electric Co Ltd | Method for producing graphene |
| CN102828161A (en) * | 2012-08-21 | 2012-12-19 | 许子寒 | Graphene production method and continuous production device of graphene |
| CN103014845A (en) * | 2012-12-31 | 2013-04-03 | 西安电子科技大学 | Method for self-assembly growth for micro-nano-scale graphene |
| CN103060907A (en) * | 2012-12-27 | 2013-04-24 | 中国科学院化学研究所 | A method of preparing single-crystal graphene on insulating materials |
-
2013
- 2013-04-25 CN CN201310147768.7A patent/CN103194795B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080107876A1 (en) * | 2006-03-27 | 2008-05-08 | Postech Foundation | Zinc Oxide Microstructures and a Method of Preparing the Same |
| CN101462717A (en) * | 2007-12-17 | 2009-06-24 | 三星电子株式会社 | Single crystalline graphene sheet and process of preparing the same |
| JP2011178644A (en) * | 2010-03-04 | 2011-09-15 | National Institute For Materials Science | Epitaxial growing method of graphene film |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| JP2012232860A (en) * | 2011-04-28 | 2012-11-29 | Fuji Electric Co Ltd | Method for producing graphene |
| CN102296361A (en) * | 2011-09-05 | 2011-12-28 | 电子科技大学 | Preparation method of single crystal graphene |
| 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 |
| CN103060907A (en) * | 2012-12-27 | 2013-04-24 | 中国科学院化学研究所 | A method of preparing single-crystal graphene on insulating materials |
| CN103014845A (en) * | 2012-12-31 | 2013-04-03 | 西安电子科技大学 | Method for self-assembly growth for micro-nano-scale graphene |
Non-Patent Citations (1)
| Title |
|---|
| MYRIANO H. OLIVEIRA JR.ET AL.: "Mono- and few-layer nanocrystalline graphene grown on Al2O3(0001) by molecular beam epitaxy", 《CARBON》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734525A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Method for preparing graphene thin film through chemical vapor deposition |
| CN104674343A (en) * | 2015-02-06 | 2015-06-03 | 北京大学 | Large single crystal graphene and preparation method thereof |
| CN105112998A (en) * | 2015-09-07 | 2015-12-02 | 北京大学 | Oxide-substrate-assisted method for quickly preparing large-size single-crystal graphene |
| WO2017041401A1 (en) * | 2015-09-07 | 2017-03-16 | Peking University | Rapid growth of large single-crystal graphene assisted by adjacent oxide substrate |
| CN105483824A (en) * | 2016-01-11 | 2016-04-13 | 信阳师范学院 | Method for preparing monocrystal double-layer graphene |
| CN108193276B (en) * | 2017-12-28 | 2020-11-10 | 中国科学院半导体研究所 | Method for preparing large-area single-orientation hexagonal boron nitride two-dimensional atomic crystal |
| CN108193276A (en) * | 2017-12-28 | 2018-06-22 | 中国科学院半导体研究所 | The method for preparing the single-orientated hexagonal boron nitride two-dimensional atomic crystal of large area |
| CN110616458A (en) * | 2019-03-07 | 2019-12-27 | 北京大学 | Method for vertical heteroepitaxy monocrystal metal film based on monocrystal copper |
| CN111243942A (en) * | 2020-01-19 | 2020-06-05 | 吉林大学 | Method for improving crystallization quality of hexagonal boron nitride by using transition metal or alloy as buffer layer |
| CN111933514A (en) * | 2020-08-12 | 2020-11-13 | 哈尔滨工业大学 | Method for preparing Ir (111) composite substrate for epitaxial single crystal diamond by electron beam evaporation process |
| CN111933514B (en) * | 2020-08-12 | 2023-02-24 | 哈尔滨工业大学 | Method for preparing Ir (111) composite substrate for epitaxial single crystal diamond by electron beam evaporation process |
| CN112899694A (en) * | 2021-01-15 | 2021-06-04 | 康斯坦丁·诺沃肖洛夫 | Method for reducing resistivity of single crystal copper wire |
| CN113148992A (en) * | 2021-03-31 | 2021-07-23 | 哈尔滨金纳科技有限公司 | Preparation method of small-size graphene |
| CN113148992B (en) * | 2021-03-31 | 2022-10-25 | 哈尔滨金纳科技有限公司 | Preparation method of small-size graphene |
| CN113737277A (en) * | 2021-09-06 | 2021-12-03 | 山东大学 | Method for preparing large-size single crystal two-dimensional material based on chemical vapor deposition |
| CN113737277B (en) * | 2021-09-06 | 2022-07-26 | 山东大学 | Method for preparing large-size single crystal two-dimensional material based on chemical vapor deposition |
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