CN105887041A - A chemical vapor deposition (CVD) method for growth of large area of graphene with low cost - Google Patents
A chemical vapor deposition (CVD) method for growth of large area of graphene with low cost Download PDFInfo
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- CN105887041A CN105887041A CN201510039341.4A CN201510039341A CN105887041A CN 105887041 A CN105887041 A CN 105887041A CN 201510039341 A CN201510039341 A CN 201510039341A CN 105887041 A CN105887041 A CN 105887041A
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Abstract
The invention relates to graphene preparation technologies, in particular to a chemical vapor deposition (CVD) method for growth of a large area of graphene with a low cost by adopting unwashed rolled metal as a base material. According to the method, the unwashed rolled metal is adopted as the base material for CVD for growth of graphene, and grease left on the surface of the metal after rolling machining is used as a carbon source of growth of graphene. The method includes the specific steps that (1) the unwashed rolled metal is adopted as the base material for CVD for growth of graphene, and the grease left on the surface of the metal is used as the carbon source of growth of graphene; and (2) the metal is directly placed in a CVD system for growth, and the large area of graphene can be formed on the surface of the metal. By the adoption of the CVD method for growth of the large area of graphene with the low cost, no extra carbon source is needed, the preparation cost is lowered accordingly, and the large area of graphene can be produced with the low cost.
Description
Technical field:
The present invention relates to the technology of preparing of Graphene, be specially one and use unwashed extruded metal as matrix
The CVD method of material low cost growing large-area Graphene.
Background technology:
Graphene is by the bi-dimensional cellular shape crystal structure of the tightly packed one-tenth of monolayer carbon atom, is to build other dimensions
The basic structural unit of Carbon Materials (zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).Graphene is unique
Crystal structure make it have electricity, calorifics and the mechanical property of excellence, as under room temperature its electron mobility is up to
200,000cm2/ V s, thermal conductivity is up to 5300W/m k, it is expected at multi-functional nanometer electronic device, electrically conducting transparent
Film, composite, catalysis material, energy storage material, field emmision material, gas sensor and gas storage etc. are led
Territory obtains extensively application.In order to comprehensively utilize numerous excellent specific properties of Graphene, the preparation side of high-quality graphene
Method is most important.(or the micromechanics stripping of adhesive tape stripping method is used from the seminar of Univ Manchester UK in 2004
From method) first separate obtain stable existence Graphene after, the method much preparing Graphene has been developed successively
Come, including chemical oxidation stripping method, separate out growth method and chemical gaseous phase deposition (CVD) method.Wherein, CVD
Method is current controlled preparation large area, the main method of high-quality graphene.By controlling temperature, carbon source and pressure
The preparation conditions such as power, it is possible to achieve at multiple substrate material surface (metal and nonmetal) growth Graphene.Closely
Several years, Graphene prepared by CVD had been used to prepare high performance transparent graphene conductive film, to touch
Touch the fields such as the photoelectric device that screen is representative and show wide application prospect.
At present, CVD growing large-area Graphene is used to there is the problem that preparation cost is higher.In order to enter one
Step promotes the application of Graphene, needs development to reduce the effective way of CVD preparation cost.Typical big face
The CVD growth method of long-pending Graphene all uses additional carbon, with Hydrocarbon such as high-purity methanes for typical case's generation
Table.The typical CVD technique of growing large-area Graphene needs to consume substantial amounts of gaseous carbon sources, and high-purity first
The hydrocarbon gas such as alkane relatively costly.It can be seen that gaseous carbon sources has become as large-area graphene preparation cost
Pith.
Summary of the invention:
It is an object of the invention to provide the CVD method of a kind of low cost growing large-area Graphene, use not
The extruded metal cleaned, as the matrix material of CVD growth Graphene, remains in after directly utilizing calendering processing
The oils and fats of metal surface is as the carbon source of growth Graphene, it is not necessary to uses additional carbon, thus reduces preparation cost.
The technical scheme is that
The CVD method of a kind of low cost growing large-area Graphene, uses unwashed extruded metal conduct
The growing substrate material of CVD growth Graphene, remains in the oils and fats of metal surface as life after utilizing calendering processing
The carbon source of long Graphene；Specifically comprise the following steps that
(1) use unwashed extruded metal as the matrix of CVD growth Graphene, the oil of its remained on surface
Fat is as the carbon source of growth Graphene；
(2) above-mentioned material is directly placed into CVD system to grow, forms large-area graphene on its surface.
The CVD method of described low cost growing large-area Graphene, the extruded metal of employing is Cu, Ni,
One of Pt, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr or two kinds
Above alloy or composite.
The CVD method of described low cost growing large-area Graphene, the growing substrate of Graphene is planar junction
Structure or be curved-surface structure.
The CVD method of described low cost growing large-area Graphene, CVD growth growth used Graphene
Carbon source is the lubricant grease used in calendering processing metal process, and Main Ingredients and Appearance is Hydrocarbon.
The CVD method of described low cost growing large-area Graphene, the equipment of CVD growth includes hot type
CVD or plasma enhanced CVD (PECVD), the technique of CVD growth includes low pressure process or normal pressure work
Skill, the atmosphere of CVD growth includes reducing atmosphere or inert atmosphere, and the mode of heating of CVD growth includes electricity
Heating, sensing heating, irradiated heat or LASER HEATING, the type of cooling of CVD growth is Slow cooling or quick
Cooling.
The CVD method of described low cost growing large-area Graphene, at the formed Graphene of growing substrate
The average number of plies is monolayer, bilayer, few layer or multilamellar, and the number of plies is less than 50 layers.
The CVD method of described low cost growing large-area Graphene, in CVD growth, by unwashed pressure
Prolong metal to put in CVD stove and grow；First by furnace chamber evacuation, until pressure is less than 1Pa, then it is passed through
Flow is hydrogen and/or the argon of 10～2000sccm of 1～500sccm, and pressure maintains 1Pa to often
Pressure；In 1～30 minute, the temperature on growing substrate surface is risen to 800～1000 DEG C, be incubated 1～60 minute；
Then cooling to room temperature with the furnace, or carry out being quickly cooled to room temperature, rate of cooling is 10～20 DEG C/sec, complete
Become CVD growth.
The feature of the present invention and providing the benefit that:
1. the present invention remains in the oils and fats carbon as growth Graphene of metal surface after directly utilizing calendering processing
Source, it is not necessary to use additional carbon, and unwashed extruded metal advantage of lower cost, therefore can reduce CVD
The cost of material of growth.
2. the method for the present invention is without using additional carbon, can reduce CVD system relevant configuration, reduce set
Standby cost.
Detailed description of the invention:
Below by embodiment, the present invention is described in more detail.
Embodiment 1
Use unskimmed rolled copper foil (25 microns of thickness) as growing substrate material.Large area Copper Foil is kept flat
On quartz plate surface, put in photoirradiation formula CVD stove and grow.First by furnace chamber evacuation, until pressure
Power is less than 1Pa, then is passed through the hydrogen that flow is 10sccm, and pressure is maintained 10Pa；In 5 minutes
The temperature of copper foil surface is risen to 1000 DEG C, cools to room temperature with the furnace after being incubated 5 minutes, complete CVD growth.
Finally, the large-area graphene that monolayer is dominant is formed on the surface of Copper Foil.
Embodiment 2
It is with the difference of embodiment 1:
Use the PECVD system of Reel-to-reel type, directly use rolled copper foil (the 35 microns of thickness) conduct of rolling
Growing substrate material, grows at 300 DEG C continuously, and the upper and lower surface of Copper Foil is respectively formed the large area that monolayer is dominant
Graphene.
Embodiment 3
Use unskimmed calendering nickel foil (50 microns of thickness) as growing substrate material.Large area nickel foil is kept flat
On quartz plate surface, put in induction heating type CVD stove and grow.First by furnace chamber evacuation, until
Pressure is less than 1Pa, then is passed through the hydrogen and the argon of 200sccm that flow is 50sccm, until pressure rises to often
Pressure；In 1 minute, furnace temperature is risen to 1000 DEG C, be incubated 1 minute；Then nickel foil is quickly cooled to room
Temperature, rate of cooling is 15 DEG C/sec, completes CVD growth.Finally, high-quality big is formed on nickel foil surface
Long-pending few layer graphene.
Embodiment result shows, the inventive method uses unwashed extruded metal as CVD growth Graphene
Matrix material, remain in the oils and fats of the metal surface carbon source as growth Graphene, nothing after utilizing calendering processing
Additional carbon need to be used, thus reduce preparation cost.Therefore, can be as a kind of low-cost production large area graphite
The method of alkene.
Claims (7)
1. the CVD method of a low cost growing large-area Graphene, it is characterised in that: use unwashed
Extruded metal, as the growing substrate material of CVD growth Graphene, remains in metal watch after utilizing calendering processing
The oils and fats in face is as the carbon source of growth Graphene；Specifically comprise the following steps that
(1) use unwashed extruded metal as the matrix of CVD growth Graphene, the oil of its remained on surface
Fat is as the carbon source of growth Graphene；
(2) above-mentioned material is directly placed into CVD system to grow, forms large-area graphene on its surface.
2., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: the extruded metal of employing is Cu, Ni, Pt, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti,
The alloy of one of Zr, V, Nb, Ta, Cr or two or more or composite.
3., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: the growing substrate of Graphene is planar structure or is curved-surface structure.
4., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: the carbon source of CVD growth growth used Graphene is the lubricant grease used in calendering processing metal process, main
Wanting composition is Hydrocarbon.
5., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: the equipment of CVD growth includes hot type CVD or plasma enhanced CVD (PECVD), CVD
The technique of growth includes low pressure process or atmospheric processes, and the atmosphere of CVD growth includes reducing atmosphere or indifferent gas
Atmosphere, the mode of heating of CVD growth includes electrical heating, sensing heating, irradiated heat or LASER HEATING, CVD
The type of cooling of growth is Slow cooling or quickly cools down.
6., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: the average number of plies at the formed Graphene of growing substrate is monolayer, bilayer, few layer or multilamellar, and the number of plies is less than
50 layers.
7., according to the CVD method of the low cost growing large-area Graphene described in claim 1, its feature exists
In: in CVD growth, unwashed extruded metal is put in CVD stove and grows；First furnace chamber is taken out
Vacuum, until pressure is less than 1Pa, then is passed through the hydrogen and/or 10～2000sccm that flow is 1～500sccm
Argon, and pressure is maintained 1Pa to normal pressure；By the temperature liter on growing substrate surface in 1～30 minute
To 800～1000 DEG C, it is incubated 1～60 minute；Then cool to room temperature with the furnace, or be quickly cooled to
Room temperature, rate of cooling is 10～20 DEG C/sec, completes CVD growth.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112397706A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海高等研究院 | Lithium ion battery cathode material structure, preparation method thereof and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013067549A (en) * | 2011-09-06 | 2013-04-18 | Waseda Univ | Method for forming thin film |
| CN103643288A (en) * | 2013-11-29 | 2014-03-19 | 中国科学院金属研究所 | Preparation method of high-quality large-size monocrystal graphene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013067549A (en) * | 2011-09-06 | 2013-04-18 | Waseda Univ | Method for forming thin film |
| CN103643288A (en) * | 2013-11-29 | 2014-03-19 | 中国科学院金属研究所 | Preparation method of high-quality large-size monocrystal graphene |
Non-Patent Citations (2)
| Title |
|---|
| WANG,HAN ETAL.: "Gigahertz Ambipolar Frequency Multiplier based on CVD Graphene", 《PROCEEDINGS OF THE IEEE INTERNATIONAL ELECTRON DEVICES》 * |
| 王文荣等: "高质量大面积石墨烯的化学气相沉积制备方法研究", 《物理学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112397706A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海高等研究院 | Lithium ion battery cathode material structure, preparation method thereof and lithium ion battery |
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