CN102092710B - Regular graphene and preparation method thereof - Google Patents

Regular graphene and preparation method thereof Download PDF

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CN102092710B
CN102092710B CN 201010594273 CN201010594273A CN102092710B CN 102092710 B CN102092710 B CN 102092710B CN 201010594273 CN201010594273 CN 201010594273 CN 201010594273 A CN201010594273 A CN 201010594273A CN 102092710 B CN102092710 B CN 102092710B
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graphene
pass
electric furnace
regular
silica tube
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CN102092710A (en
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武斌
耿德超
黄丽平
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Institute of Chemistry CAS
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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

A kind of regular graphene and preparation method thereof
Technical field
The present invention relates to a kind of regular graphene and preparation method thereof.
Background technology
Graphene, i.e. the monoatomic layer of graphite, be carbon atom by the two-dirnentional structure of honeycomb arrangement, also be the elementary cell that consists of other low dimension carbon material 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 huge application prospect have caused the research boom in the 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 the 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 with Graphene of 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: put into the anhydrous reactor of anaerobic with tinsel or with the substrate of metal catalyst, make tinsel or substrate temperature reach 800~1050 ℃ (preferred 900~1050 ℃), then pass into carbon source in the described reactor and react, obtain having the Graphene of regular morphology.
Described tinsel can directly be bought.Described substrate with metal catalyst can be prepared according to existing method, as can be with metal by any is deposited on the substrate that obtains on the substrate with metal catalyst in lower 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 passes into described carbon source is 5-100sccm; In order to obtain the Graphene of desirable isogonism hexagonal structure, the flow that passes into 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 the difficulties such as gold and silver, copper with the sour catalyzer that reacts in the preparation process, remove catalyzer by itself and salts solution (such 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 the 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 with the substrate of metal catalyst, 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 regular graphene among the embodiment 1.
Fig. 3 is by the Raman spectrum of chemical Vapor deposition process at copper surface deposition regular graphene among the embodiment 1
Fig. 4 is by the atomic force microscopy of chemical Vapor deposition process at copper surface deposition regular graphene among the embodiment 1.
Fig. 5 is the electron scanning micrograph of removing the regular graphene behind the copper among the embodiment 1.
Fig. 6 is transmission electron microscope and the selected area electron diffraction photo of removing 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 regular graphene among the embodiment 2.
Fig. 8 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition regular graphene among the embodiment 3.
Fig. 9 is by the electron scanning micrograph of chemical Vapor deposition process at copper surface deposition regular 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 preparation of the first step, catalyzer:
Substrate is used oven for drying after deionized water, ethanol, the acetone ultrasonic cleaning successively, then 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, or directly use commercial tinsel (such as gold and silver, copper, iron, cobalt, nickel etc.) as catalyzer.
Second step, vapor phase growing apparatus with depositing the substrate of metal or tinsel and place the middle part of clean silica tube, are put into electric furnace with silica tube as shown in Figure 1, make the middle part of silica tube just be positioned at the central zone of electric furnace.With mechanical pump the air in the silica tube and moisture are extracted out first, then in silica tube, passed into 100~2000sccm non-oxidizing gas (such as hydrogen, argon gas etc.) 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, pass into carbonaceous material (such 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 pass into carbon compound, close simultaneously electric furnace, continue to pass into 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, then cleans post-drying with deionized water; When adopting the difficulties such as gold and silver, copper with the sour catalyzer that reacts, by removing catalyzer with salts solution generation replacement(metathesis)reaction (such as iron nitrate, iron(ic) chloride etc.).
Embodiment 1, preparation regular graphene
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 places the middle part of clean silica tube with described Copper Foil, and silica tube is put into electric furnace, makes the middle part of silica tube be positioned at the central zone of electric furnace, then passes into the argon gas of 120sccm in silica tube, after 5~10 minutes, stops to pass into argon gas.Opening vacuum pump begins to vacuumize, when in the reaction chamber during 3~10 handkerchief of pressure position, close vacuum pump, pass into again the hydrogen gas mixture of the argon gas of 100sccm and 300sccm until the reaction chamber internal pressure is consistent with external atmosphere pressure, stop to pass into 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 ℃, passed into 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 pass into methane, close simultaneously electric furnace, continuing to pass into 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 represents multilayer, blue line represents 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.Atomic force microscopy 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, then clean oven dry with deionized water.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 Graphene.
Embodiment 2, preparation regular graphene
The preparation method is substantially with embodiment 1, difference is: when furnace temperature reaches 1000 ℃, pass into the methane of 20sccm 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 desirable isogonism hexagonal structure.This fact has ubiquity, that is to say, along with the increase of carbon source flow velocity or say equivalently the increase of the speed of growth, the shape of Graphene moves to more and more irregular direction.
Embodiment 3, preparation regular graphene
The preparation method is substantially with example 1, and difference is: when the central zone temperature of electric furnace reaches 1050 ℃, and then pass into 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 4,900 ℃ of lower preparation regular graphenes
The preparation method is substantially with example 1, and difference is: when the central zone temperature of electric furnace reaches 900 ℃, and then pass into 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 (1)

1. a method for preparing the Graphene with regular morphology comprises the steps:
The first step, oven for drying after the Copper Foil of the purity 99.8% that 25um is thick deionized water, ethanol, the acetone ultrasonic cleaning;
Second step places the middle part of clean silica tube with described Copper Foil, and silica tube is put into electric furnace, makes the middle part of silica tube be positioned at the central zone of electric furnace, then passes into the argon gas of 120sccm in silica tube, after 5 ~ 10 minutes, stops to pass into argon gas; Opening vacuum pump begins to vacuumize, when pressure in the reaction chamber is 3 ~ 10 handkerchief, close vacuum pump, pass into again the hydrogen gas mixture of the argon gas of 100sccm and 300sccm until the reaction chamber internal pressure is consistent with external atmosphere pressure, stop to pass into 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 ℃, passed into 10sccm methane as carbon source in described carrier gas, reaction begins to carry out;
The 4th step after reaction is carried out 40 minutes, stopped to pass into methane, closed simultaneously electric furnace, continued to pass into 300sccm hydrogen and made temperature drop to room temperature, obtained Graphene;
The 5th step, the substrate that deposits Graphene is put into 1 mole every liter iron nitrate solution immersion removal in 60 minutes copper, then clean oven dry with deionized water;
Described Graphene with regular morphology is the Graphene with hexagonal configuration.
CN 201010594273 2010-12-17 2010-12-17 Regular graphene and preparation method thereof Expired - Fee Related CN102092710B (en)

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