CN102092710A - Regular graphene and preparation method thereof - Google Patents
Regular graphene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses graphene with a regular shape and a preparation method thereof. The graphene with a regular shape is prepared by the chemical vapor deposition method and comprises the following steps: placing a metal foil or a substrate with a metal catalyst in a reactor without oxygen and water to ensure that the temperature of the metal foil or the substrate reaches 800-1050 DEG C, and then introducing a carbon source in the reactor to react and obtain the graphene with a regular shape. The obtained graphene in the invention has an equiangular hexagonal structure; and the method in the invention is convenient to operate, is simple and practical and can be used in mass production.
Description
Technical field
The present invention relates to a kind of regular Graphene and preparation method thereof.
Background technology
Graphene, promptly the monoatomic layer of graphite is the two-dirnentional structure of carbon atom by honeycomb arrangement, also is the elementary cell of other low dimension carbon material of formation such as soccerballene, carbon nanotube.According to the number of plies, Graphene can be divided into single-layer graphene, double-layer graphite alkene, few layer graphene.The research of Graphene is of long duration, but the Graphene of real independent stable existence then is to be obtained by the high oriented graphite of tape stripping by the Geim of Univ Manchester UK etc.After Graphene is found, because its excellent performance and great application prospect have caused the research boom in fields such as physics and Materials science.But controlledly synthesis has the problem of the grapheme material of specific function and application still not to solve, and these problems comprise perfect degree of the lattice of the controlled big area Graphene of the number of plies, patterning, Graphene and the grapheme material with regular geometric shapes.Owing to these reasons, the research of Graphene still rests on the fundamental research field.At present, the main method of preparation Graphene has mechanically peel graphite method (Novoselov, K.S.; Geim, A.K.; Morozov, S.V.; Jiang, D.; Zhang, Y.; Dubonos, S.V.; Grigorieva, I.V.; Firsov, A.A., Science 2004,306,666), epitaxy (Science 2006,312 for C.Berger, Z.M.Song, 1191), graphite oxidation restore method (McAllister, M.J.; Li, J., Adamson, D.H.; Schniepp, H.C.; Abdala, A.A, Liu, J.; Herrera-Alonso, M.; Milius, D.L.; Car, R.; Prudhomme, R.K.; Aksay, I.A., Chem.Mater.2007,19,4396) and chemical gaseous phase depositing process (Li, X.S.; Cai, W.W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S.K.; Colombo, L.; Ruoff, R.S.Science 2009,324,1312-1314.).But how extensive, controlled syntheticly have the Graphene on regular geometric border also from undiscovered and report.
Chemical vapour deposition is a kind of deposition technique the most frequently used in the semi-conductor industry.The principle of this method is the mode by chemical reaction, utilize the various energy such as heating, plasma excitation or optical radiation, in reactor, make the chemical substance of gaseous state or steam condition on gas phase or gas-solid interface, form the technology of solid deposited thing through chemical reaction.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of graphene with regular morphology.
Graphene with regular morphology provided by the present invention is to adopt chemical Vapor deposition process, be prepared according to the method that may further comprise the steps: tinsel or the substrate that has a metal catalyst are put into the anhydrous reactor of anaerobic, make tinsel or substrate temperature reach 800～1050 ℃ (preferred 900～1050 ℃), in described reactor, feed carbon source then and react, obtain having the Graphene of regular morphology.
Described tinsel can directly be bought.The described substrate that has metal catalyst can be prepared according to existing method, as can be with metal by any is deposited on the substrate that obtains having metal catalyst on the substrate in following six kinds of methods: chemical Vapor deposition process, physical vaporous deposition, vacuum thermal evaporation method, magnetron sputtering method, plasma enhanced chemical vapor deposition method, electrochemical plating and print process.
Wherein, described metal can be a kind of or its arbitrary combination in copper, gold and silver, nickel, cobalt and the iron.
Described carbon source specifically can be a kind of or its arbitrary combination in methane, carbon monoxide, methyl alcohol, acetylene, ethanol, benzene, toluene, hexanaphthene and the phthalocyanine.
Graphene with regular morphology provided by the present invention is the Graphene with hexagonal structure.
The flow that feeds described carbon source is 5-100sccm; In order to obtain the Graphene of ideal isogonism hexagonal structure, the flow that feeds described carbon source is preferably 5-20sccm.The reaction times of described reaction is 0.5～1000 minute, preferred 20-60 minute.As a rule, in 100-200 nm/minute scope, its final size depends on the reaction times to this equilateral hexagon Graphene along the speed of growth of diagonal.
Aforesaid method comprises that also the Graphene to preparation carries out the step of purifying, to remove metal catalyst.
When adopting iron, cobalt in the preparation process, when nickel is made catalyzer, can passing through acid solution (example hydrochloric acid, sulfuric acid, nitric acid etc.) reaction and remove; When adopting difficulties such as gold and silver, copper and the sour catalyzer that reacts in the preparation process, remove catalyzer by itself and salts solution (as iron nitrate, iron(ic) chloride etc.) generation replacement(metathesis)reaction.
The present invention prepares the Graphene with regular morphology by chemical Vapor deposition process, and this method is easy and simple to handle, and simple and feasible can be used for scale operation.
Description of drawings
Fig. 1 is the chemical vapor deposition unit synoptic diagram, and wherein, 1 is tinsel or the substrate that has metal catalyst, and 2 is tube furnace, and 3 is silica tube.
Fig. 2 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 1.
Fig. 3 is by the Raman spectrum of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 1
Fig. 4 is by the atomic force microscope photo of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 1.
Fig. 5 is for removing the electron scanning micrograph of the regular Graphene behind the copper among the embodiment 1.
Fig. 6 is for removing the transmission electron microscope and the selected area electron diffraction photo of the regular Graphene behind the copper among the embodiment 1.
Fig. 7 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 2.
Fig. 8 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 3.
Fig. 9 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition rule Graphene among the embodiment 4.
Embodiment
Below by specific embodiment method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The present invention will be described in detail below in conjunction with accompanying drawing:
The first step, Preparation of catalysts:
Substrate is used oven for drying after deionized water, ethanol, the acetone ultrasonic cleaning successively, deposit layer of metal by deposition techniques such as chemical vapour deposition, physical vapor deposition, vacuum thermal evaporation, magnetron sputtering, plasma enhanced chemical vapor deposition, electrochemical process or printings at substrate surface then, or directly use commercial tinsel (as gold and silver, copper, iron, cobalt, nickel etc.) as catalyzer.
Second step, vapor phase growing apparatus place the middle part of clean silica tube with depositing the substrate of metal or tinsel as shown in Figure 1, and silica tube is put into electric furnace, make the middle part of silica tube be positioned at the central zone of electric furnace just.With mechanical pump air in the silica tube and moisture are extracted out earlier, in silica tube, fed 100～2000sccm non-oxidizing gas (as hydrogen, argon gas etc.) then after 1～1000 minute, begin heating;
The 3rd the step, when the temperature of electric furnace central zone reaches 800～1050 ℃, in non-oxidizing gas, feed carbonaceous material (as carbon monoxide, methane, acetylene, ethanol, benzene, toluene, hexanaphthene, phthalocyanine etc.) as carbon source, reaction begins to carry out, and carbon generates Graphene in the catalyst surface deposition;
After the 4th step, reaction are carried out 0.5～1000 minute, stop to feed carbon compound, close electric furnace simultaneously, continue to feed non-oxidizing gas refrigeration to room temperature;
The 5th goes on foot, carries out purification process:
When the catalyzer that adopts iron, cobalt, nickel etc. to react with acid, purification process is substrate to be put into acid solution (example hydrochloric acid, sulfuric acid, nitric acid etc.) soak and went out catalyzer in 0.5～1000 minute, cleans the back oven dry with deionized water then; When adopting difficulty such as gold and silver, copper, by removing catalyzer with salts solution generation replacement(metathesis)reaction (as iron nitrate, iron(ic) chloride etc.) with the sour catalyzer that reacts.
The first step, oven for drying after the Copper Foil that 25um is thick (purity 99.8%) deionized water, ethanol, the acetone ultrasonic cleaning.
Second step placed the middle part of clean silica tube with described Copper Foil, and silica tube is put into electric furnace, made the middle part of silica tube be positioned at the central zone of electric furnace, fed the argon gas of 120sccm then in silica tube, after 5～10 minutes, stopped to feed argon gas.Opening vacuum pump begins to vacuumize, when in the reaction chamber during 3～10 handkerchiefs of pressure position, close vacuum pump, the hydrogen gas mixture that feeds the argon gas of 100sccm and 300sccm again is consistent with external atmosphere pressure until the reaction chamber internal pressure, stop to feed argon gas, only with 300sccm hydrogen as carrier gas, ventilate after 10 minutes, begin the heating;
The 3rd step when the temperature of electric furnace central zone reaches 1000 ℃, fed 10sccm methane as carbon source in described carrier gas, reaction begins to carry out;
The 4th step, after reaction is carried out 40 minutes, stop to feed methane, close electric furnace simultaneously, continuing to feed 300sccm hydrogen makes temperature drop to room temperature, the electron scanning micrograph of product as shown in Figure 2, there is homodisperse isogonism hexagon material on the copper surface as can be observed from Figure, this material is Graphene.The Raman spectrum of product as shown in Figure 3, wherein red line is represented multilayer, blue line is represented individual layer, black line represents not have the copper zone of Graphene.Above result proves that isogonism hexagon Graphene is high-quality single or multiple lift.The atomic force microscope photo is observed the regular hexagonal material as shown in Figure 4 from figure, this material is regular Graphene;
The 5th step, the described substrate that deposits Graphene is put into 1 mole every liter iron nitrate solution immersion removal in 60 minutes copper, clean oven dry with deionized water then.The electron scanning micrograph of product can be found the regular hexagonal structure as shown in Figure 5 from figure, this material is Graphene; The transmission electron microscope photo (left side) of product and selected area electron diffraction photo (right side) as shown in Figure 6, product is two-dimentional isogonism hexagon regular texture as can be observed from Figure, illustrates that product is a Graphene.
The preparation method is substantially with embodiment 1, difference is: when furnace temperature reaches 1000 ℃, the methane that feeds 20sccm is as carbon source, the electron scanning micrograph of its product as shown in Figure 7, from figure, still can see the hexagonal structure of two dimension, but its shape begins to depart from ideal isogonism hexagonal structure.This fact has ubiquity, that is to say, along with the increase of carbon source flow velocity or say the increase of the speed of growth equivalently, the shape of Graphene moves to more and more irregular direction.
The preparation method is substantially with example 1, and difference is: when the central zone temperature of electric furnace reaches 1050 ℃, and then feed 5sccm methane as carbon source.The electron scanning micrograph of product is seen the regular hexagonal structure as shown in Figure 8 from figure, illustrate that product is regular Graphene.
Embodiment prepares regular Graphene down for 4,900 ℃
The preparation method is substantially with example 1, and difference is: when the central zone temperature of electric furnace reaches 900 ℃, and then feed 50sccm methane as carbon source.The electron scanning micrograph of product is seen the regular hexagonal structure as shown in Figure 9 from figure, illustrate that product is regular Graphene.
Claims (8)
1. method for preparing Graphene with regular morphology, adopt chemical Vapor deposition process to be prepared, may further comprise the steps: tinsel or the substrate that has a metal catalyst are put into the anhydrous reactor of anaerobic, make tinsel or substrate temperature reach 800～1050 ℃, in described reactor, feed carbon source then and react, obtain having the Graphene of regular morphology.
2. method according to claim 1 is characterized in that: described metal is a kind of or its arbitrary combination in copper, gold and silver, nickel, cobalt and the iron.
3. method according to claim 1 and 2 is characterized in that: described carbon source is a kind of or its arbitrary combination in methane, carbon monoxide, methyl alcohol, acetylene, ethanol, benzene, toluene, hexanaphthene and the phthalocyanine.
4. according to each described method among the claim 1-3, it is characterized in that: the flow that feeds described carbon source in the described reaction is 5-100sccm; Be preferably 5-50sccm.
5. according to each described method among the claim 1-4, it is characterized in that: the reaction times of described reaction is 0.5～1000 minute, preferred 20-60 minute.
6. according to each described method among the claim 1-5, it is characterized in that: described Graphene with regular morphology is the Graphene with hexagonal structure.
7. according to each described method among the claim 1-6, it is characterized in that: described method comprises that also the Graphene with regular morphology to preparation carries out the step that purifying is removed metal catalyst.
8. the Graphene for preparing according to each described method among the claim 1-7 with regular morphology.
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| CN102849961A (en) * | 2011-07-01 | 2013-01-02 | 中央研究院 | Method for growing carbon film or inorganic material film on substrate |
| CN102874801A (en) * | 2012-10-15 | 2013-01-16 | 中国科学院上海微***与信息技术研究所 | Preparation method for graphene |
| CN103145117A (en) * | 2013-02-28 | 2013-06-12 | 中国科学院化学研究所 | Method for preparing graphene |
| WO2013104141A1 (en) * | 2012-01-11 | 2013-07-18 | 中国科学院上海微***与信息技术研究所 | Method for using carbon source having multiple benzene rings to grow graphene over large area by chemical vapor deposition at low temperature |
| CN103407996A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | High conductivity graphene preparation method |
| CN103409728A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Method for preparing graphene through chemical vapor deposition |
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| CN103449428A (en) * | 2013-09-10 | 2013-12-18 | 常州二维碳素科技有限公司 | Graphene growing device and method |
| CN103958730A (en) * | 2011-11-29 | 2014-07-30 | 三星泰科威株式会社 | Thin metal film for synthesizing graphene and graphene manufacturing method using the same |
| CN103981507A (en) * | 2014-05-21 | 2014-08-13 | 电子科技大学 | Graphene preparation method |
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| CN104925798A (en) * | 2015-06-29 | 2015-09-23 | 南昌大学 | Triangular graphene preparing method |
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| CN106044751A (en) * | 2016-05-28 | 2016-10-26 | 王奉瑾 | Catalytic preparation method of graphene |
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Inventor after: Wu Bin Inventor after: Geng Dechao Inventor after: Huang Liping Inventor after: Xue Yunzhou Inventor after: Zheng Jian Inventor after: Chen Jianyi Inventor after: Yu Gui Inventor after: Liu Yunqi Inventor before: Wu Bin Inventor before: Geng Dechao Inventor before: Huang Liping |
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| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WU BIN GENG DECHAO HUANG LIPING TO: WU BIN GENG DECHAO HUANG LIPING XUE YUNZHOU ZHENG JIAN CHEN JIANYI YU GUI LIU YUNQI |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130123 Termination date: 20151217 |
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