CN103964417B - A kind of preparation method of the doped graphene containing Ge element - Google Patents
A kind of preparation method of the doped graphene containing Ge element Download PDFInfo
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- CN103964417B CN103964417B CN201310034451.2A CN201310034451A CN103964417B CN 103964417 B CN103964417 B CN 103964417B CN 201310034451 A CN201310034451 A CN 201310034451A CN 103964417 B CN103964417 B CN 103964417B
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Abstract
The present invention is applied to chemosynthesis technical field, there is provided a kind of preparation method of doped graphene, prepares the doped graphene containing Ge element using chemical vapour deposition technique, the described method comprises the following steps：Catalytic substrate is put into the reactor of vacuum, the material containing carbon and Ge element is then passed through into the reactor, the doped graphene containing Ge element is made.The doped graphene obtained using the compound containing Ge element as dopant, do not destroyed for the hexagonal structure of graphene, and the carrier concentration of the doped graphene containing Ge element obtained after adulterating is high, mobility is high.
Description
Technical field
The invention belongs to chemosynthesis technical field, is related to a kind of preparation method of the doped graphene containing Ge element.
Background technology
As the tightly packed two dimensional crystal material formed of single layer of carbon atom, graphene has high carrier mobility
Numerous excellent physicochemical properties such as rate, high light transmittance, high intensity, have emphatically in fields such as electronics, the energy, biological and chemicals
The potential application wanted.The method for preparing high-quality graphene at present mainly has adhesive tape stripping method, carborundum or metal surface extension
Can growth method and chemical vapour deposition technique, but the single-layer graphene prepared is zero gap semiconductor, Effective Regulation its electricity
Learn characteristic and decide application future of this new material in fields such as microelectronics.
Doping is considered as to regulate and control one of effective means of graphene electrical properties, but the complete bi-dimensional cellular shape of graphene
Structure brings very big difficulty to its doping.Common doping way mainly includes physical doping (metal surface doping), Yi Jihua
Learn doping.Wherein, metal surface doping uses metal nanoparticle, is vaporized on graphenic surface, contacts the metal of graphene
With graphene charge-exchange occurs for nano particle so as to realize the regulation and control to graphene carrier concentration.Chemical doping then it is mostly be
In the preparation process of graphene, doping nitrogen-atoms etc. replaces the carbon atom of graphene, and realizes displacement and adulterate, and forms electric charge and turns
Move.
Metal surface is unstable and right in Shortcomings in current doping method, wherein metal surface doping method
The ability of regulation and control of graphene carrier is weaker.And the chemical doping of the nitrogen-atoms used at present, for the surface texture of graphene
Severity is destroyed, although carrier concentration increases, mobility is greatly reduced.
The content of the invention
The embodiment of the present invention aims to overcome that problems of the prior art, there is provided a kind of doping containing Ge element
The preparation method of graphene.
The embodiment of the present invention is achieved in that a kind of preparation method of the doped graphene containing Ge element, using chemistry
Vapour deposition process prepares the doped graphene containing element, the described method comprises the following steps：Catalytic substrate is put into the anti-of vacuum
Answer in device, the compound containing carbon and germane is then passed through into the reactor, the doping stone containing Ge element is made
Black alkene.
In a preferred embodiment, methods described also includes electropolishing processing catalytic substrate surface.
In a preferred embodiment, the catalytic substrate is copper sheet, and the electropolishing processing catalytic substrate step includes：Match somebody with somebody
Put electropolishing solution；, with being inserted as the copper sheet of negative electrode in electropolishing solution, it is powered as the target copper sheet of anode and keeps
Voltage stabilization 1.5~6 volts 1 minute；Target copper sheet is taken out from electropolishing solution, cleaned up with deionized water, then
Rinsed with absolute ethyl alcohol, last nitrogen drying.
In a preferred embodiment, the electropolishing solution is deionized water, phosphoric acid, ethanol, isopropanol, urea configuration and
Into mixed solution.
In a preferred embodiment, the copper thickness as negative electrode is 6~200 μm.
In a preferred embodiment, the compound being passed through into the reactor containing carbon and germane, is obtained
Doped graphene containing Ge element includes step：It is passed through the compound of carbon elements so that the compound of carbon elements is in copper
Surface cracks and grows graphene；Change the chemical combination logistics capacity of carbon elements, while be passed through the compound containing germane, be made germanic
The doped graphene of element.
In a preferred embodiment, the compound of the carbon elements is methane, the step：It is passed through the change of carbon elements
Compound so that the compound of carbon elements cracks on copper surface and grows graphene；Change the chemical combination logistics capacity of carbon elements, together
When be passed through the compound containing germane, the doped graphene containing Ge element is made to be passed through 1sccm methane 30 seconds so that carbon source is being urged
Change substrate surface to crack and grow graphene, change methane flow to 3sccm, while be passed through 0.1~0.5sccm germanes, keep
1000 degree 10 minutes, be made the doped graphene containing Ge element.
In a preferred embodiment, the compound containing carbon be carbon monoxide, acetylene, ethanol, benzene, toluene,
Any of hexamethylene.
In a preferred embodiment, the reactor is vacuum tube furnace.
In an embodiment of the present invention, there is following technique effect：Obtained using containing germane compound as dopant
Doped graphene, do not destroyed for the hexagonal structure of graphene, and the doped graphene containing Ge element that obtains after adulterating
Carrier concentration it is high, mobility is high.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention is a kind of preparation method of the doped graphene containing Ge element, is prepared using chemical vapour deposition technique germanic
The doped graphene of element, methods described comprise the following steps：Catalytic substrate is put into the reactor of vacuum, then to described
The compound containing carbon and germane is passed through in reactor, the doped graphene containing germane is made.
Before preparation, also with electropolishing handle catalytic substrate surface the step of.
The compound being passed through into the reactor containing carbon and germane, obtains the doping stone containing Ge element
Black alkene includes step：It is passed through the compound of carbon elements so that the compound of carbon elements cracks on copper surface and grows graphite
Alkene；Change the chemical combination logistics capacity of carbon elements, while be passed through the compound containing germane, the doped graphene containing Ge element is made.
The compound containing carbon can be carbon monoxide, methane, acetylene, ethanol, benzene, toluene, hexamethylene etc..
In an embodiment of the present invention, the preparation method comprises the following steps：
One, electropolishing processing catalytic substrate surface：
1, configure electropolishing solution：The solution can use 1000ml deionized waters, 500ml phosphoric acid, 500ml ethanol,
100ml isopropanols, 10g urea are configured to mixed solution；
2, using thickness be 6~200 μm of copper sheet as negative electrode, it is necessary to which the target copper sheet handled inserts electric throwing as anode
In light solution, be powered keep voltage stabilization 1.5~6 volts 1 minute.
3, target copper sheet is taken out from electropolishing solution, cleaned up with deionized water, then rinsed with absolute ethyl alcohol, most
Nitrogen dries up afterwards.
Two, prepare the doped graphene containing Ge element：
1, copper sheet good handled by step 1 is put into vacuum tube furnace constant temperature zone；
2, vacuum tube is evacuated in base vacuum, about 0.2~0.5 Pascal with vavuum pump, then be passed through 10sccm hydrogen；
3, heating, vacuum tube furnace is kept for 5 minutes at such a temperature to 1000 degree, is removed the oxide on copper sheet surface and is moved back
Fire；
4, it is passed through 1sccm methane 30 seconds so that carbon source cracks on copper sheet surface and grows graphene；
5, change methane flow to 3sccm, while 0.1~0.5sccm germanes are passed through, it is maintained at 1000 degree 10 minutes, makes
The doped graphene of element must be contained；
6, stop heating, vacuum tube furnace is naturally cooled into normal temperature；
7, it is passed through argon gas and destroys vacuum, treat that vacuum reaches 1 atmospheric pressure in pipe, vacuum tube furnace can be opened and take out sample
Product.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (7)
1. a kind of preparation method of the doped graphene containing Ge element, it is characterised in that prepared and contained using chemical vapour deposition technique
The doped graphene of Ge element, the described method comprises the following steps：Catalytic substrate is put into the reactor of vacuum, then to institute
State and the compound containing carbon and germane is passed through in reactor, the doped graphene containing Ge element is made；
The compound being passed through into the reactor containing carbon and Ge element, obtains the doped graphite containing Ge element
Alkene includes step：It is passed through the compound of carbon elements so that the compound of carbon elements cracks on copper surface and grows graphene；
Change the chemical combination logistics capacity of carbon elements, while be passed through the compound containing germane, the doped graphene containing Ge element is made；It is described
The compound of carbon elements is methane, is specially to be passed through 1sccm methane 30 seconds so that carbon source is cracked and given birth on catalytic substrate surface
Long graphene, change methane flow to 3sccm, while be passed through 0.1~0.5sccm germanes, be maintained at 1000 degree 10 minutes, be made
Doped graphene containing Ge element.
2. the method as described in claim 1, it is characterised in that methods described also includes electropolishing processing catalytic substrate surface.
3. method as claimed in claim 2, it is characterised in that the catalytic substrate is copper sheet, the electropolishing processing catalysis
Substrate step includes：Configure electropolishing solution；Will be molten with inserting electropolishing as the copper sheet of negative electrode as the target copper sheet of anode
In liquid, be powered and keep voltage stabilization 1.5~6 volts 1 minute；Target copper sheet is taken out from electropolishing solution, spend from
Sub- water cleans up, then is rinsed with absolute ethyl alcohol, last nitrogen drying.
4. method as claimed in claim 3, it is characterised in that the electropolishing solution is deionized water, phosphoric acid, and ethanol is different
Propyl alcohol, the mixed solution that urea configuration forms.
5. method as claimed in claim 3, it is characterised in that the copper thickness as negative electrode is 6~200 μm.
6. the method as described in claim 1, it is characterised in that the compound containing carbon be carbon monoxide, acetylene,
Any of ethanol, benzene, toluene, hexamethylene substitute the methane in claim 1.
7. the method as described in claim 1, it is characterised in that the reactor is vacuum tube furnace.
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| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102745678A (en) * | 2012-07-12 | 2012-10-24 | 浙江大学 | Method for preparing nitrogen-doped graphene by utilizing plasma sputtering |
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| US8361853B2 (en) * | 2010-10-12 | 2013-01-29 | International Business Machines Corporation | Graphene nanoribbons, method of fabrication and their use in electronic devices |
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Patent Citations (4)
| 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 |
| 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 |
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