CN103964417A - Preparation method of doped graphene containing germanium - Google Patents
Preparation method of doped graphene containing germanium Download PDFInfo
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- CN103964417A CN103964417A CN201310034451.2A CN201310034451A CN103964417A CN 103964417 A CN103964417 A CN 103964417A CN 201310034451 A CN201310034451 A CN 201310034451A CN 103964417 A CN103964417 A CN 103964417A
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Abstract
The invention is applicable to the technical field of chemical synthesis, and provides a preparation method of doped graphene. A chemical vapor deposition method is employed to prepare doped graphene containing germanium. The method comprises the following steps: placing a catalytic substrate into a reactor in a vacuum, and then introducing materials containing carbon and the germanium into the reactor, so as to prepare doped graphene containing germanium. The doped graphene obtained by using the compound containing germanium as a doping agent has no damaged hexagonal structure, and the doped graphene containing germanium has high carrier concentration and high mobility.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of preparation method of the doped graphene containing element Ge.
Background technology
As the tightly packed two dimensional crystal material forming of monolayer carbon atom, Graphene has the physicochemical property of numerous excellences such as high carrier mobility, high light transmittance, high strength, at electronics, the energy, there is important potential application in the fields such as biological and chemical.The method of preparing at present high-quality graphene mainly contains tape stripping method, silicon carbide or metallic surface epitaxial growth method and chemical Vapor deposition process, but the single-layer graphene of preparing is zero gap semiconductor, can determine the application future of this novel material in fields such as microelectronics by its electrology characteristic of Effective Regulation.
Doping is considered to regulate and control one of effective means of Graphene electrical properties, but the complete bi-dimensional cellular shape structure of Graphene is brought very large difficulty to its doping.Common doping way mainly comprises physical doping (metallic surface doping), and chemical doping.Wherein, the metallic surface doping metal nanoparticles that adopt more, evaporation is on Graphene surface, thus metal nanoparticle and the Graphene generation charge-exchange of contact Graphene realize the regulation and control to Graphene carrier concentration.Chemical doping is is mostly in the preparation process of Graphene, and doping nitrogen-atoms etc. is replaced the carbon atom of Graphene, and realizes displacement doping, forms electric charge and shifts.
Shortcomings in current adulterating method, wherein in the adulterating method of metallic surface, metallic surface is unstable, and to the ability of regulation and control of Graphene current carrier a little less than.And the chemical doping of the nitrogen-atoms using at present destroys severity for the surface tissue of Graphene, although carrier concentration increases, mobility declines greatly.
Summary of the invention
The object of the embodiment of the present invention is to overcome problems of the prior art, and a kind of preparation method of the doped graphene containing element Ge is provided.
The embodiment of the present invention is to realize like this, a kind of preparation method of the doped graphene containing element Ge, adopt the doped graphene of chemical Vapor deposition process preparation containing element Ge, said method comprising the steps of: the reactor of catalytic substrate being put into vacuum, then in described reactor, pass into the compound that contains carbon and element Ge, make the doped graphene that contains element Ge.
In a preferred embodiment, described method also comprises electropolishing processing catalytic substrate surface.
In a preferred embodiment, described catalytic substrate is copper sheet, and described electropolishing is processed catalytic substrate step and comprised: configuration electropolishing solution; Using as the target copper sheet of anode with insert in electropolishing solution as the copper sheet of negative electrode, energising and sustaining voltage be stabilized in 1.5～6 volts 1 minute; Target copper sheet is taken out from electropolishing solution, clean up with deionized water, then rinse with dehydrated alcohol, last nitrogen dries up.
In a preferred embodiment, described electropolishing solution is deionized water, phosphoric acid, and ethanol, Virahol, urea configures the mixing solutions forming.
In a preferred embodiment, the described copper sheet thickness as negative electrode is 6～200 μ m.
In a preferred embodiment, describedly in described reactor, pass into the compound that contains carbon and element Ge, the doped graphene that obtains containing element Ge comprises step: pass into the compound of carbon elements, make the compound of carbon elements at copper surface cracking growing graphene; The compound flow that changes carbon elements passes into the compound containing element Ge simultaneously, makes the doped graphene containing element Ge.
In a preferred embodiment, the compound of described carbon elements is that methane, the described compound containing element Ge are germane, described step: pass into the compound of carbon elements, make the compound of carbon elements at copper surface cracking growing graphene; Change the compound flow of carbon elements, pass into the compound containing element Ge simultaneously, make the doped graphene that contains element Ge for passing into 1sccm methane 30 seconds, make carbon source at catalytic substrate surface cracking growing graphene, change methane flow to 3sccm, pass into 0.1～0.5sccm germane simultaneously, remain on 1000 degree 10 minutes, make the doped graphene containing element Ge.
In a preferred embodiment, the compound that contains carbon described in is any in carbon monoxide, methane, acetylene, ethanol, benzene, toluene, hexanaphthene.
In a preferred embodiment, the material that contains element Ge described in is germane.
In a preferred embodiment, described reactor is vacuum tube furnace.
In an embodiment of the present invention, there is following technique effect: the doped graphene that uses germanic element compound to obtain as doping agent, hexagonal structure for Graphene does not destroy, and the carrier concentration of the doped graphene containing element Ge obtaining after doping is high, and mobility is high.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The present invention is a kind of preparation method of the doped graphene containing element Ge, adopt the doped graphene of chemical Vapor deposition process preparation containing element Ge, described method comprises the steps: catalytic substrate to put into the reactor of vacuum, then in described reactor, pass into the compound that contains carbon and element Ge, make the doped graphene that contains element Ge.
Before preparation, also there is electropolishing and process the step on catalytic substrate surface.
Describedly in described reactor, pass into the compound that contains carbon and element Ge, the doped graphene that obtains containing element Ge comprises step: pass into the compound of carbon elements, make the compound of carbon elements at copper surface cracking growing graphene; The compound flow that changes carbon elements passes into the compound containing element Ge simultaneously, makes the doped graphene containing element Ge.
The described compound that contains carbon can be carbon monoxide, methane, acetylene, ethanol, benzene, toluene, hexanaphthene etc.
The described compound that contains element Ge can be germane etc.
In an embodiment of the present invention, described preparation method comprises the steps:
One, catalytic substrate surface is processed in electropolishing:
1, configuration electropolishing solution: described solution can adopt 1000ml deionized water, 500ml phosphoric acid, 500ml ethanol, 100ml Virahol, 10g urea is configured to mixing solutions;
2, using thickness be the copper sheet of 6～200 μ m as negative electrode, need target copper sheet to be processed as anode, insert in electropolishing solution, energising sustaining voltage be stabilized in 1.5～6 volts 1 minute.
3, target copper sheet is taken out from electropolishing solution, clean up with deionized water, then rinse with dehydrated alcohol, last nitrogen dries up.
Two, preparation contains the doped graphene of element Ge:
1, the copper sheet that step 1 is handled well is put into vacuum tube furnace constant temperature region;
2, valve tube is evacuated in base vacuum with vacuum pump, approximately 0.2～0.5 pascal, then pass into 10sccm hydrogen;
3, heating, vacuum tube furnace to 1000 degree keeps 5 minutes at this temperature, removes oxide compound the annealing on copper sheet surface;
4, pass into 1sccm methane 30 seconds, make carbon source at copper sheet surface cracking growing graphene;
5, change methane flow to 3sccm, pass into 0.1～0.5sccm germane simultaneously, remain on 1000 degree 10 minutes, make the doped graphene containing element Ge;
6, stop heating, vacuum tube furnace is naturally cooled to normal temperature;
7, pass into argon gas and destroy vacuum, treat that in pipe, vacuum reaches 1 normal atmosphere, just can open vacuum tube furnace and take out sample.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the preparation method containing the doped graphene of element Ge, it is characterized in that, adopt the doped graphene of chemical Vapor deposition process preparation containing element Ge, said method comprising the steps of: the reactor of catalytic substrate being put into vacuum, then in described reactor, pass into the compound that contains carbon and element Ge, make the doped graphene that contains element Ge.
2. the method for claim 1, is characterized in that, described method also comprises electropolishing processing catalytic substrate surface.
3. method as claimed in claim 2, is characterized in that, described catalytic substrate is copper sheet, and described electropolishing is processed catalytic substrate step and comprised: configuration electropolishing solution; Using as the target copper sheet of anode with insert in electropolishing solution as the copper sheet of negative electrode, energising and sustaining voltage be stabilized in 1.5 ~ 6 volts 1 minute; Target copper sheet is taken out from electropolishing solution, clean up with deionized water, then rinse with dehydrated alcohol, last nitrogen dries up.
4. method as claimed in claim 3, is characterized in that, described electropolishing solution is deionized water, phosphoric acid, and ethanol, Virahol, urea configures the mixing solutions forming.
5. method as claimed in claim 3, is characterized in that, the described copper sheet thickness as negative electrode is 6 ~ 200 μ m.
6. the method for claim 1, it is characterized in that, describedly in described reactor, pass into the compound that contains carbon and element Ge, the doped graphene that obtains containing element Ge comprises step: pass into the compound of carbon elements, make the compound of carbon elements at copper surface cracking growing graphene; The compound flow that changes carbon elements passes into the compound containing element Ge simultaneously, makes the doped graphene containing element Ge.
7. method as claimed in claim 6, it is characterized in that, the compound of described carbon elements is that methane, the described compound containing element Ge are germane, and described step passes into the compound of carbon elements, makes the compound of carbon elements at copper surface cracking growing graphene; Change the compound flow of carbon elements, pass into the compound containing element Ge simultaneously, make the doped graphene that contains element Ge for passing into 1sccm methane 30 seconds, make carbon source at catalytic substrate surface cracking growing graphene, change methane flow to 3sccm, pass into 0.1 ~ 0.5sccm germane simultaneously, remain on 1000 degree 10 minutes, make the doped graphene containing element Ge.
8. the method for claim 1, is characterized in that, described in contain carbon compound be any in carbon monoxide, methane, acetylene, ethanol, benzene, toluene, hexanaphthene.
9. the method for claim 1, is characterized in that, described in contain element Ge material be germane.
10. the method for claim 1, is characterized in that, described reactor is vacuum tube furnace.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082415A (en) * | 2017-02-28 | 2017-08-22 | 杭州格蓝丰纳米科技有限公司 | A kind of preparation method of Ge-doped grapheme material |
| CN111979525A (en) * | 2020-07-06 | 2020-11-24 | 上海交通大学 | Preparation method of high-conductivity graphene/copper composite wire |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966987A (en) * | 2010-10-13 | 2011-02-09 | 重庆启越涌阳微电子科技发展有限公司 | Fractal graphene material with negative electron affinity as well as preparation method and application thereof |
| KR20110132804A (en) * | 2010-06-03 | 2011-12-09 | 한국과학기술원 | Doped 2-dimensional carbon material for oxygen reduction and alcohol tolerant properties as a cathode of polymer electrolyte fuel cell |
| CN102400109A (en) * | 2011-11-11 | 2012-04-04 | 南京航空航天大学 | Method for growing large area of layer-number-controllable graphene at low temperature through chemical vapor deposition (CVD) method by using polystyrene solid state carbon source |
| US20120085991A1 (en) * | 2010-10-12 | 2012-04-12 | International Business Machines Corporation | Graphene nanoribbons, method of fabrication and their use in electronic devices |
| CN102745678A (en) * | 2012-07-12 | 2012-10-24 | 浙江大学 | Method for preparing nitrogen-doped graphene by utilizing plasma sputtering |
-
2013
- 2013-01-29 CN CN201310034451.2A patent/CN103964417B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110132804A (en) * | 2010-06-03 | 2011-12-09 | 한국과학기술원 | Doped 2-dimensional carbon material for oxygen reduction and alcohol tolerant properties as a cathode of polymer electrolyte fuel cell |
| US20120085991A1 (en) * | 2010-10-12 | 2012-04-12 | International Business Machines Corporation | Graphene nanoribbons, method of fabrication and their use in electronic devices |
| CN101966987A (en) * | 2010-10-13 | 2011-02-09 | 重庆启越涌阳微电子科技发展有限公司 | Fractal graphene material with negative electron affinity as well as preparation method and application thereof |
| CN102400109A (en) * | 2011-11-11 | 2012-04-04 | 南京航空航天大学 | Method for growing large area of layer-number-controllable graphene at low temperature through chemical vapor deposition (CVD) method by using polystyrene solid state carbon source |
| CN102745678A (en) * | 2012-07-12 | 2012-10-24 | 浙江大学 | Method for preparing nitrogen-doped graphene by utilizing plasma sputtering |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082415A (en) * | 2017-02-28 | 2017-08-22 | 杭州格蓝丰纳米科技有限公司 | A kind of preparation method of Ge-doped grapheme material |
| CN111979525A (en) * | 2020-07-06 | 2020-11-24 | 上海交通大学 | Preparation method of high-conductivity graphene/copper composite wire |
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| CN103964417B (en) | 2018-03-16 |
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