CN102259849A - Method for preparing graphene by utilizing solid carbon source - Google Patents
Method for preparing graphene by utilizing solid carbon source Download PDFInfo
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- CN102259849A CN102259849A CN2011101536351A CN201110153635A CN102259849A CN 102259849 A CN102259849 A CN 102259849A CN 2011101536351 A CN2011101536351 A CN 2011101536351A CN 201110153635 A CN201110153635 A CN 201110153635A CN 102259849 A CN102259849 A CN 102259849A
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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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- 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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- 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
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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
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention relates to a method for preparing graphene by utilizing a solid carbon source. The method comprises the following steps of: (1) coating organic polymer on the surface of a metal substrate as the solid carbon source, then homogenizing the metal substrate on a spin coater, and then heating the homogenized metal substrate; and (2) placing the metal substrate coated with the solid carbon source heated in the step (1) in a vacuum reaction furnace, injecting protective gas into a vacuum cavity under the condition that oxygen in the vacuum cavity is removed, heating to the temperature of 800-1100 DEG C, and maintaining the highest temperature for 1-100 minutes and maintaining the flow of the protective gas so as to obtain the metal substrate deposited with the graphene. The method relates to no dangerous gas and is a safe graphene preparation technique.
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.
4. metal substrate chemical Vapor deposition process
Chemical Vapor deposition process is to utilize the atomic structure extension of substrate to go out Graphene, at first allows carbon atom at high temperature (1000
oC) be dissolved under in the metal substrate, the carbon dissolution degree of metal reduces and reduces along with temperature.After the substrate cooling, carbon atom reaches hypersaturated state in metal, and a large amount of carbon atoms of dissolved will precipitate into the Graphene that the metallic surface forms controllable thickness before.
This method can arrive the individual layer or the multi-layer graphene of high quality big area (cm size), is present of paramount importance a kind of graphene preparation method.Yet the process need of preparation Graphene is used inflammable gas, and for example hydrogen and methane have certain danger.
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 solid-state carbon source prepares the method for Graphene, and step is as follows:
(1) is coated with organic polymer (0.1-10 milliliter PMMA or PDMS) on the metal substrate surface as solid-state carbon source, (rotating speed is 500-10000 rev/min then above-mentioned metal substrate to be placed homogenize on the photoresist spinner, time is 10 seconds-30 minutes), again will be through the metal substrate heating (Heating temperature 30-200 degree centigrade, the time is 10 seconds-60 minutes) of homogenize; (2) metal substrate with the solid-state carbon source of spraying after the heating of step (1) places the vacuum reaction stove; in removing vacuum chamber under the situation of oxygen; to protect gas to inject vacuum chamber; and be warming up to 800-1100 degree centigrade; remained on top temperature 1-100 minute; keep shield gas flow rate simultaneously, 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 10
-6Torr.
The method of taking out the metal substrate of deposition Graphene is: close shielding gas valve, vacuum pump, with rare gas element the vacuum reaction stove is filled to 1 atmospheric pressure state, take out the metal substrate of deposition Graphene then.
The flow velocity of shielding gas is 1-100 sccm, and purity is higher than 99.99%.
Described metal substrate is Copper Foil or nickel foil.Organic polymer as solid-state carbon source is PMMA or PDMS.Protection gas is that volume ratio 99.99% above argon gas or volume ratio are the mixed gas of 97% argon gas and 3% hydrogen, does not have combustibility, explosivity, and production process is safe and reliable.
The present invention develops and safer, the better solid-state carbon source Graphene technology of preparing of operability on the basis of chemical deposition technique.At metal substrate surface spraying organic film, under hot environment and under the reducing gas protection, organic film decomposites carbon atom under the katalysis of metal substrate.Carbon atom forms graphene film in the metallic surface crystallization.This method does not relate to dangerous gas, is a kind of safe Graphene technology of preparing.
Compared with the prior art gained Graphene product of the present invention has the following advantages:
(1) the Graphene product has very high-quality; (2) size more than the size of Graphene product can reach centimetre; (3) the Graphene product has fabulous light transmission; (4) thickness of Graphene is controlled from the individual layer to the multilayer; (5) Graphene is produced the gases used explosivity that do not possess, and production process is safe and reliable.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 prepared Graphene of the present invention.
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.
Shown in Figure 1; the Graphene preparation system that this reaction unit is made up of protection airshed meter 1, inert gas flowmeter 2, silica tube 4, tube furnace 5, vacuumometer 6 and substrate 7; silica tube 4 places tube furnace 5; one side of silica tube 4 links to each other with the rare gas element gas cylinder with shielding gas respectively by protection airshed meter 1, inert gas flowmeter 2, 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 operating method is consistent with above-mentioned tube furnace.
Embodiment 1
The present invention adopts the solid-state carbon source of pyrolytic decomposition, and crystallization forms graphene film on metal substrate, comprises following preparation process:
1. get 20 millimeters square smooth metal copper foils, be fixed on the sheet glass;
2. sheet glass is fixed on the centrifugal photoresist spinner;
3. drip 0.1 milliliter of solid-state carbon source polymethylmethacrylate of PMMA(in the spray of metal substrate surface).
4. setting the photoresist spinner rotating speed is 500 rev/mins, and the time is 30 minutes.
5. take off the metal substrate on the sheet glass, be heated to 30 degrees centigrade on heating plate, the time is 60 minutes.
6. the metal substrate 7 that will spray solid-state carbon source places silica tube 4;
7. the air pressure with silica tube 4 is evacuated to highest attainable vacuum state 4 * 10
-2Holder (Torr);
8. set gas flow 5 sccm of inert gas flowmeter 2, rare gas element is injected in the silica tube 4;
9. after 10 minutes, close the air intake valve of inert gas flowmeter 2, the air pressure of silica tube 4 is evacuated to the limit 4 * 10
-2Holder (Torr);
10. the operation steps of repeating step 8 and step 9 is 2～3 times; Up to the remnant oxygen in the silica tube 4 is driven totally to oxygen partial pressure less than 10
-6Torr;
11. setting the gas flow of protection airshed meter 1 is 5 sccm, will protect gas to continue to inject silica tube 4;
12. the temperature of tube furnace 5 is elevated to 800 degrees centigrade, and the time length that remains on top temperature is 100 minutes;
13. tube furnace 5 temperature are reduced to room temperature.
14. close protection airshed meter 1 air intake valve, vacuum pump, setting inert gas flowmeter 2 flows is 100sccm, with rare gas element the air pressure of silica tube 4 is filled to 1 atmospheric pressure state;
15. open silica tube 4, take out the metal substrate 7 that has deposited Graphene.
Described shielding gas is that volume ratio is the mixed gas of 97% argon gas and 3% hydrogen.
Embodiment 2
The present invention adopts the solid-state carbon source of pyrolytic decomposition, and crystallization forms graphene film on metal substrate, comprises following preparation process:
1. get 50 millimeters square smooth metal nickel foils, be fixed on the sheet glass;
2. sheet glass is fixed on the centrifugal photoresist spinner;
3. drip 10 milliliters of solid-state carbon source polydimethylsiloxanes of PDMS(in the spray of metal substrate surface).
4. setting the photoresist spinner rotating speed is 10000 rev/mins, and the time is 30 seconds.
5. take off the metal substrate on the sheet glass, heating is 200 degrees centigrade on heating plate, and the time is 10 seconds.
6. the metal substrate 7 that will spray solid-state carbon source places silica tube 4;
7. the air pressure with silica tube 4 is evacuated to highest attainable vacuum state 8 * 10
-2Holder (Torr);
8. set the gas flow 100sccm of inert gas flowmeter 2, rare gas element is injected in the silica tube 4;
9. after 10 minutes, close the air intake valve of inert gas flowmeter 2, the air pressure of silica tube 4 is evacuated to the limit 8 * 10
-2Holder (Torr);
10. the operation steps of repeating step 8 and step 9 is 2～3 times; Up to the remnant oxygen in the silica tube 4 is driven totally to oxygen partial pressure less than 10
-6Torr;
11. set gas flow 100 sccm of protection airshed meter 1, will protect gas to continue to be injected in the vacuum chamber;
12. the temperature of tube furnace 5 is elevated to 1100 degrees centigrade, and the time length that remains on top temperature is 5 minutes;
13. tube furnace 5 temperature are reduced to room temperature.
14. close protection airshed meter 1 air intake valve, vacuum pump 8, setting inert gas flowmeter 2 flows is 50 sccm, with rare gas element the air pressure of silica tube 4 is filled to 1 atmospheric pressure state;
15. open silica tube 4, take out the metal substrate 7 that has deposited Graphene.
Described shielding gas is the argon gas of volume ratio more than 99.99%.
Embodiment 3
The present invention adopts the solid-state carbon source of pyrolytic decomposition, and crystallization forms graphene film on metal substrate, comprises following preparation process:
1. get 30 millimeters square smooth metal copper foils, be fixed on the sheet glass;
2. sheet glass is fixed on the centrifugal photoresist spinner;
3. drip 5 milliliters of solid-state carbon source polymethylmethacrylates of PMMA(in the spray of metal substrate surface).
4. setting the photoresist spinner rotating speed is 5000 rev/mins, and the time is 10 minutes.
5. take off the metal substrate on the sheet glass, be heated to 100 degrees centigrade on heating plate, the time is 10 minutes.
6. the metal substrate 7 that will spray solid-state carbon source places silica tube 4;
7. the air pressure with silica tube 4 is evacuated to highest attainable vacuum state 6 * 10
-2Holder (Torr);
8. set gas flow 50 sccm of inert gas flowmeter 2, rare gas element is injected in the silica tube 4;
9. after 10 minutes, close the air intake valve of inert gas flowmeter 2, the air pressure of silica tube 4 is evacuated to the limit 6 * 10
-2Holder (Torr);
10. the operation steps of repeating step 8 and step 9 is 2～3 times; Up to the remnant oxygen in the silica tube 4 is driven totally to oxygen partial pressure less than 10
-6Torr;
11. setting the gas flow of protection airshed meter 1 is 50 sccm, will protect gas to continue to inject silica tube 4;
12. the temperature of tube furnace 5 is elevated to 950 degrees centigrade, and the time length that remains on top temperature is 55 minutes;
13. tube furnace 5 temperature are reduced to room temperature.
14. close protection airshed meter 1 air intake valve, vacuum pump, setting inert gas flowmeter 2 flows is 75sccm, with rare gas element the air pressure of silica tube 4 is filled to 1 atmospheric pressure state;
15. open silica tube 4, take out the metal substrate 7 that has deposited Graphene.
Described shielding gas is that volume ratio is the mixed gas of 97% argon gas and 3% hydrogen.
Accompanying drawing 2 is Raman spectrums of present embodiment 3 gained Graphenes, and as can be seen from this figure: there are two intrinsic Raman peaks-G peaks and 2D peak (1580 cm-1 and 2680 cm-1) of Graphene in (1); (2) intensity at 2D peak is approximately the twice at G peak, illustrates that the gained Graphene is a monoatomic layer; (3) – D peak, defective peak (1350 cm-1) almost can not differentiate, and illustrates 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 (5)
1. a solid-state carbon source prepares the method for Graphene, and it is characterized in that: step is as follows,
(1) be coated with organic polymer as solid-state carbon source on the metal substrate surface, then above-mentioned metal substrate placed homogenize on the photoresist spinner, again will be through the metal substrate heating of homogenize;
(2) metal substrate with the solid-state carbon source of spraying after the heating of step (1) places the vacuum reaction stove; in removing vacuum chamber under the situation of oxygen; to protect gas to inject vacuum chamber; and be warming up to 800-1100 degree centigrade; kept top temperature 1-100 minute; keep the protection airshed simultaneously, promptly get the metal substrate that deposits Graphene.
2. solid-state carbon source according to claim 1 prepares the method for 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 10
-6Torr.
3. solid-state carbon source according to claim 1 prepares the method for Graphene, it is characterized in that: described metal substrate is Copper Foil or nickel foil.
4. solid-state carbon source according to claim 1 prepares the method for Graphene, it is characterized in that: described organic polymer as solid-state carbon source is PMMA or PDMS.
5. solid-state carbon source according to claim 1 prepares the method for Graphene, it is characterized in that: described protection gas is that volume ratio is the mixed gas of 97% argon gas and 3% hydrogen.
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|---|---|---|---|
| CN2011101536351A CN102259849A (en) | 2011-06-09 | 2011-06-09 | Method for preparing graphene by utilizing solid carbon source |
| PCT/CN2012/076190 WO2012167700A1 (en) | 2011-06-09 | 2012-05-29 | Method for preparing graphene by using solid carbon source |
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| CN102583347A (en) * | 2012-02-17 | 2012-07-18 | 北京化工大学 | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material |
| CN102683217A (en) * | 2012-05-24 | 2012-09-19 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphite-based double-gate MOSFET (Metal-Oxide-Semiconductor Field Effect Transistor) |
| WO2012167700A1 (en) * | 2011-06-09 | 2012-12-13 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by using solid carbon source |
| CN102828244A (en) * | 2012-09-24 | 2012-12-19 | 中国科学院上海微***与信息技术研究所 | Layer-number-controllable graphite film based on nickel-copper composite substrate and preparation method of film |
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| CN103265024A (en) * | 2013-06-08 | 2013-08-28 | 新疆师范大学 | Method for preparing graphene compound |
| CN103420355A (en) * | 2012-05-22 | 2013-12-04 | 海洋王照明科技股份有限公司 | Method for preparing carbon nanometer walls from solid carbon source |
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