CN102220566A - Method for preparing single-layer or multi-layer graphene through chemical vapor deposition - Google Patents
Method for preparing single-layer or multi-layer graphene through chemical vapor deposition Download PDFInfo
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- CN102220566A CN102220566A CN2011101534854A CN201110153485A CN102220566A CN 102220566 A CN102220566 A CN 102220566A CN 2011101534854 A CN2011101534854 A CN 2011101534854A CN 201110153485 A CN201110153485 A CN 201110153485A CN 102220566 A CN102220566 A CN 102220566A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention discloses a method for preparing single-layer or multi-layer graphene through chemical vapor deposition, and relates to a method for preparing a graphene material. The method comprises the following steps of: placing a metal substrate in a vacuum tubular furnace or a vacuum atmosphere furnace; injecting hydrogen into a vacuum cavity under the situation of removing the oxygen in the vacuum cavity; heating to 800-1,100 DEG C; and injecting a carbon source gas into the vacuum cavity to obtain the metal substrate for depositing graphene. According to the method disclosed by the invention, a graphene film is deposited by cracking methane or other carbon source gases on the metal substrate (such as a copper foil or a nickel foil and the like) at a high temperature by using the chemical vapor deposition method; and therefore, the invention provides a method for preparing the single-layer or multi-layer graphene with an ultra-large area.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material.
Background technology
Graphene, English name Graphene is that carbon atom is arranged the two-dimensional crystal lattice structure that forms according to hexagonal.As monolayer carbon atomic plane material, Graphene can obtain by peeling off graphite material.This graphite crystal film is after 2004 are found by the scientist of University of Manchester, and Graphene just becomes the focus that scientific circles and industry member are paid close attention to.The thickness of Graphene has only 0.335 nanometer, is not only in the known materials the thinnest a kind of, also very firmly hard; As simple substance, the speed that it at room temperature transmits electronics than known all conductor and semi-conductor all fast (in the Graphene travelling speed of electronics reached the light velocity 1/300).Because the weird atom structure of Graphene, wherein the behavior of current carrier (electronics and hole) must just can be described with relativistic quantum mechanics (relativistic quantum mechanics).Because its high electron mobility and high transmission rate, Graphene may be used in various areas of information technology, for example is applied on the flat-panel monitor as transparency conductive electrode, perhaps is applied on high frequency/RF transistors as channel layer.Simultaneously, as the monolayer carbon atomic structure, the theoretical specific surface area of Graphene is up to 2630 m
2/ g.So high specific surface area makes becomes extremely promising energy storage active material with the material based on Graphene, makes grapheme material to be applied at storage hydrogen, new type lithium ion battery, ultracapacitor or fuel cell.
Following several preparation method is arranged at present:
1. slight rubbing manipulation or tear tape are sent out (pasting HOPG)
This method is simple, obtains high-quality Graphene easily.But productive rate is extremely low, can only obtain the some Graphenes that micron is square on a Si substrate usually.Therefore this method only is applicable to the prepared in laboratory Graphene, is not suitable for large-scale industrialization production.
2. heat the SiC method
This method is to remove Si by heating monocrystalline 6H-SiC, decomposites the Graphene lamella on monocrystalline (0001) face.Detailed process is: the sample that will obtain through oxygen or hydrogen etching processing by the electron-bombardment heating, is removed oxide compound under high vacuum.After determining that with Auger electron spectrum the oxide compound on surface is removed fully, constant temperature was 1 minute to 20 minutes after sample heating made it temperature and be increased to 1250 ~ 1450 ℃, thereby form graphite linings as thin as a wafer, through exploration in a few years, people such as Berger can controllably prepare individual layer or multi-layer graphene.Because its thickness is determined that by Heating temperature the preparation big area has the graphite of single thickness
Alkene is difficulty relatively.
This method can realize large size, and the preparation of high quality Graphene is a kind of to realizing the very important preparation method of practical application of graphene device, and shortcoming is that SiC is too expensive, and the Graphene that obtains is difficult to transfer on other substrates.
3. chemical dispersion method
Graphite oxide is that graphite is at H
2SO
4, HNO
3, HClO
4Under the effect Deng strong oxidizer, or under the electrochemistry peroxidation, after hydrolysis, form.Graphite oxide is a stratiform covalent compound equally, and it is 0.335nm that interfloor distance is approximately 0.8nm(graphite) different according to the preparation method.It is generally acknowledged, contain in the graphite oxide-C-OH ,-C-O-C, even-groups such as COOH.Different with graphite, because the existence of polar group, oxidized graphite flake layer has the characteristic of stronger hydrophilic or polar solvent.Therefore, graphite oxide as peeling off under the action of ultrasonic waves, forms mono-layer graphite oxide alkene (graphene oxide) in external force in water or in other polar solvent.After making graphene oxide, make made graphene oxide deoxidation greying again by chemical reduction again, but its electroconductibility of recuperation section when keeping its how much patterns.
This method is dissociated into mono-layer graphite with natural graphite powder in oxidation and reduction process.Its product has long-pending (〉 700 m of quite high specific surface area
2/ g), and process is simple relatively, so this method relatively is fit to large-scale industrialization production grapheme material.But be its electroconductibility of partial reduction (having destroyed the high electron mobility of Graphene itself) in redox processes.
Summary of the invention
The technical problem to be solved in the present invention is the defective that overcomes existing graphene preparation method, and a kind of method for preparing overlarge area individual layer or multi-layer graphene film is provided.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
A kind of chemical vapour deposition prepares the method for individual layer and multi-layer graphene, metal substrate is placed vacuum tube furnace or vacuum atmosphere oven, in removing vacuum chamber under the situation of oxygen, hydrogen is injected vacuum chamber, and be warming up to 800-1100 degree centigrade, again carbon-source gas is injected vacuum chamber, promptly get the metal substrate that deposits Graphene.
Further, remove that the method for oxygen is in the vacuum chamber:
(1) air pressure with tube furnace or atmosphere furnace is evacuated to highest attainable vacuum state 4～8 * 10
-2Torr;
(2) with gas flow 1-100 sccm purity being higher than 99.99% rare gas element is injected in the vacuum chamber;
(3) close the rare gas element air intake valve, the air pressure of tube furnace or atmosphere furnace is evacuated to the limit 4～8 * 10
-2Torr;
(4) repetitive operation step (2) and step (3) 2～3 times, until the remnant oxygen in tube furnace or the atmosphere furnace is removed to oxygen partial pressure less than 1 * 10
-6Torr.
The method of taking out the metal substrate of deposition Graphene is: close hydrogen and carbon-source gas valve, vacuum pump, with rare gas element tube furnace or atmosphere furnace air pressure are filled to an atmospheric pressure state, take out the metal substrate of deposition Graphene then.
The flow velocity of hydrogen and carbon-source gas is 1-100 sccm, and purity is higher than 99.99%.
Described carbon-source gas is for only containing the organic gas of hydrocarbon atom, and preferred carbon-source gas is a methane.
Described metal substrate is Copper Foil, nickel foil, rubidium paper tinsel or ruthenium paper tinsel.
The present invention adopts chemical Vapor deposition process, goes up Pintsch process methane or other carbon-source gas in metal substrate (Copper Foil or nickel foil etc.), and deposition obtains graphene film, thereby a kind of method for preparing overlarge area individual layer or multi-layer graphene film is provided.
Compared with the prior art the present invention has the following advantages:
(1) Graphene product defects peak is low, has high crystal mass; (2) size more than the size of Graphene product (domain) can reach centimetre; (3) the Graphene product has fabulous light transmission (transmissivity is better than 97%); (4) thickness of Graphene is controlled from the individual layer to the multilayer, obtains the monoatomic layer Graphene easily.The product that present method obtains can be applicable to a plurality of technical fields, comprises flat pannel display, high frequency/RF transistors.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used from explanation the present invention with embodiments of the invention one, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the structural representation of the reaction unit of embodiment of the invention 1-3 employing;
Fig. 2 is the Raman spectrogram of the embodiment of the invention 3 prepared Graphenes.
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in qualification the present invention.
As shown in Figure 1, the chemical gas-phase deposition system that this reaction unit is made up of inert gas flowmeter 1, hydrogen flowmeter 2, carbon-source gas under meter 3, silica tube 4, tube furnace 5, vacuumometer 6, substrate 7, silica tube 4 places tube furnace 5, one side of silica tube 4 links to each other with rare gas element, hydrogen and carbon-source gas gas cylinder respectively by inert gas flowmeter 1, hydrogen flowmeter 2, carbon-source gas under meter 3, and the opposite side of silica tube 4 links to each other with vacuum pump with vacuumometer 6 successively.
Certainly, silica tube and tube furnace can change an atmosphere furnace that has than large space into, and its operation steps is identical with above-mentioned tube furnace.
Embodiment 1
On Copper Foil, prepare graphene film by chemical Vapor deposition process, comprise following preparation process:
1. get 25 micron thickness Copper Foil substrates 7 and place silica tube 4;
2. open vacuum pump the air pressure of silica tube 4 is evacuated to highest attainable vacuum state 4 * 10
-2Holder (Torr);
3. inert gas flowmeter 1 is set at 5 sccm, and argon gas is injected in the vacuum chamber;
4. after 5 minutes, close inert gas flowmeter 1 valve, the air pressure of tube furnace 5 is evacuated to the limit 8 * 10
-2Holder (Torr);
5. the operation steps of repeating step (3) and step (4) is 3 times; Up to the remnant oxygen of silica tube 4 is driven totally to oxygen partial pressure less than 1 * 10
-6Torr;
6. hydrogen flowmeter 2 is set at 5 sccm, and hydrogen is injected in the vacuum chamber;
7. the temperature with tube furnace 5 is elevated to 1000 degrees centigrade;
8. carbon-source gas under meter 3 is set 5 sccm, and methane is injected in the vacuum chamber;
9. the temperature of tube furnace 5 is reduced to room temperature.
10. close hydrogen flowmeter 2, carbon-source gas under meter 3 valves and vacuum pump.Inert gas flowmeter 1 is set at 50sccm, with argon gas silica tube 4 air pressure is filled to an atmospheric pressure state;
11. open silica tube 4 vacuum interfaces, take out the Copper Foil substrate 7 that has deposited Graphene.
Embodiment 2
On the nickel film, prepare graphene film by chemical Vapor deposition process, comprise following preparation process:
1. by magnetron sputtering evaporation 500nm thickness nickel film on silicon substrate 7; Get the silicon substrate 7 that steams the Ni plated film and place silica tube 4;
2. open vacuum pump the air pressure of silica tube 4 is evacuated to highest attainable vacuum state 8 * 10
-2Holder (Torr);
3. inert gas flowmeter 1 is set at 50 sccm, and helium is injected in the vacuum chamber;
4. after 5 minutes, close inert gas flowmeter 1 valve, the air pressure of tube furnace 5 is evacuated to the limit 4 * 10
-2Holder (Torr);
5. the operation steps of repeating step (3) and step (4) is 2 times; Up to the remnant oxygen of silica tube 4 is driven totally to oxygen partial pressure less than 1 * 10
-6Torr;
6. hydrogen flowmeter 2 is set at 50 sccm, and hydrogen is injected in the vacuum chamber;
7. the temperature with tube furnace 5 is elevated to 900 degrees centigrade;
8. carbon-source gas under meter 3 is set 50 sccm, and ethane is injected in the vacuum chamber;
9. the temperature of tube furnace 5 is reduced to room temperature.
10. close hydrogen flowmeter 2, carbon-source gas under meter 3 valves and vacuum pump.Inert gas flowmeter 1 is set at 100 sccm, with helium silica tube 4 air pressure is filled to an atmospheric pressure state;
11. open silica tube 4 vacuum interfaces, take out the nickel film substrate 7 that has deposited Graphene.
Embodiment 3
On the nickel film, prepare graphene film by chemical Vapor deposition process, comprise following preparation process:
1. by magnetron sputtering evaporation 500nm thickness nickel film on silicon substrate 7; Get the silicon substrate 7 that steams the Ni plated film and place silica tube 4;
2. open vacuum pump the air pressure of silica tube 4 is evacuated to highest attainable vacuum state 6 * 10
-2Holder (Torr);
3. inert gas flowmeter 1 is set at 100 sccm, and nitrogen is injected in the vacuum chamber;
4. after 5 minutes, close inert gas flowmeter 1 valve, the air pressure of tube furnace 5 is evacuated to the limit 6 * 10
-2Holder (Torr);
5. the operation steps of repeating step (3) and step (4) is 2 times; Up to the remnant oxygen of silica tube 4 is driven totally to oxygen partial pressure less than 1 * 10
-6Torr;
6. hydrogen flowmeter 2 is set at 100sccm, and hydrogen is injected in the vacuum chamber;
7. the temperature with tube furnace 5 is elevated to 800 degrees centigrade;
8. carbon-source gas under meter 3 is set 100sccm, and ethene is injected in the vacuum chamber;
9. the temperature of tube furnace 5 is reduced to room temperature.
10. close hydrogen flowmeter 2, carbon-source gas under meter 3 valves and vacuum pump.Inert gas flowmeter 1 is set at 75 sccm, with nitrogen silica tube 4 air pressure is filled to an atmospheric pressure state;
11. open silica tube 4 vacuum interfaces, take out the nickel film substrate 7 that has deposited Graphene.
Accompanying drawing 2 is Raman spectrums of present embodiment 3 gained Graphenes, and as can be seen from this figure: there are two the intrinsic Raman peaks-G peaks and 2D peak (1580 cm of Graphene in (1)
-1With 2680 cm
-1); (2) intensity at 2D peak is approximately the twice at G peak, illustrates that the gained Graphene is a monoatomic layer; (3) defective Feng – D peak (1350 cm
-1) almost can not differentiate, illustrate that the gained Graphene has high crystal mass.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a chemical vapour deposition prepares the method for individual layer and multi-layer graphene, it is characterized in that: the transition metal substrate is placed the vacuum reaction stove, in removing vacuum chamber under the situation of oxygen, hydrogen is injected vacuum chamber, and be warming up to 800-1100 degree centigrade, again carbon-source gas is injected vacuum chamber, keep hydrogen flowing quantity simultaneously, promptly get the metal substrate that deposits Graphene after 1-100 minute.
2. chemical vapour deposition according to claim 1 prepares the method for individual layer and multi-layer graphene, it is characterized in that: the method for removing oxygen in the vacuum chamber is:
(1) air pressure with tube furnace or atmosphere furnace is evacuated to highest attainable vacuum state 4～8 * 10
-2Torr;
(2) with gas flow 1-100 sccm purity being higher than 99.99% rare gas element is injected in the vacuum chamber;
(3) close the rare gas element air intake valve, the air pressure of tube furnace or atmosphere furnace is evacuated to the limit 4～8 * 10
-2Torr;
(4) repetitive operation step (2) and step (3) 2～3 times, until the remnant oxygen in tube furnace or the atmosphere furnace is removed to oxygen partial pressure less than 1 * 10
-6Torr.
3. chemical vapour deposition according to claim 1 prepares the method for individual layer and multi-layer graphene, it is characterized in that: the method for taking out the metal substrate of deposition Graphene is: close hydrogen and carbon-source gas valve, vacuum pump, with rare gas element tube furnace or atmosphere furnace air pressure are filled to an atmospheric pressure state, take out metal substrate then.
4. chemical vapour deposition according to claim 1 prepares the method for individual layer and multi-layer graphene, it is characterized in that: the flow velocity of hydrogen and carbon-source gas is 1-100 sccm, and purity is higher than 99.99%.
5. described chemical vapour deposition prepares the method for individual layer and multi-layer graphene according to claim 1-4, it is characterized in that: described carbon-source gas is for only containing the organic gas of hydrocarbon atom.
6. chemical vapour deposition according to claim 5 prepares the method for individual layer and multi-layer graphene, it is characterized in that: described carbon-source gas is a methane.
7. described chemical vapour deposition prepares the method for individual layer and multi-layer graphene according to claim 1-4, and it is characterized in that: described metal substrate is Copper Foil, nickel foil, rubidium paper tinsel or ruthenium paper tinsel.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101534854A CN102220566A (en) | 2011-06-09 | 2011-06-09 | Method for preparing single-layer or multi-layer graphene through chemical vapor deposition |
| PCT/CN2012/076194 WO2012167701A1 (en) | 2011-06-09 | 2012-05-29 | Chemical vapor deposition method for producing monolayer and multilayer graphene |
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