CN107161985A - A kind of method of low-temperature epitaxy graphene - Google Patents
A kind of method of low-temperature epitaxy graphene Download PDFInfo
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- CN107161985A CN107161985A CN201710517063.8A CN201710517063A CN107161985A CN 107161985 A CN107161985 A CN 107161985A CN 201710517063 A CN201710517063 A CN 201710517063A CN 107161985 A CN107161985 A CN 107161985A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of method of low-temperature epitaxy graphene, comprise the following steps：1）With crystalloid sodium chloride（NaCl）For substrate, magnetically controlled sputter method pre-deposition a layer thickness is used for 10nm Zn films in advance thereon.2）The NaCl substrates that above-mentioned pre-deposition there are Zn films are placed in tube type resistance furnace, 300 350 DEG C are heated to, H2 CH4 N2 is passed through for reacting gas, reacts 3.5 hours.3）After reaction terminates, power supply is closed, continues to be passed through H2 gas, using H2 air coolings, sample is quickly cooled to room temperature, obtain required product graphene.The graphene according to made from above-mentioned low-temperature growth method, is two-dimensional layered structure, is grown in vertically on substrate, and is interconnected to form loose structure, and appearance structure is uniform.Growth temperature of the present invention is reduced to 300 DEG C, and this is the low-down temperature of graphene growth；And the obtained graphene pattern of growth is uniform, porous with specific surface area is done to obtain, and has broad prospect of application in ultracapacitor.
Description
Technical field
The present invention relates to the technical field of technical field of graphene preparation, especially graphene low-temperature epitaxy.
Background technology
Graphene is most burning the hotest new material in the recent decade, is a kind of typical two-dimension nano materials, each side
Excellent performance, almost as a kind of universal material.
The growing method of graphene has many kinds, can be divided mainly into two aspects：First, gas phase process, the graphite of growth
Alkene is individual layer or less several layers of, is commonly used to the fields such as microelectronics, photoelectron, optics, electricity；Second, liquid phase process,
The graphene of growth is the stratified material with the more number of plies, is commonly used to the neck such as catalysis, lithium ion battery, ultracapacitor
Domain.
In method of vapor-phase growing, common growth course is：Using Cu or SiC pieces as substrate, CH4 and H2 are reaction gas
Body, the growth more than 1000 DEG C is, it is necessary to which very high temperature, energy consumption is big, and yields poorly.
Recent years, one of the target that people pursue is to realize the low-temperature gaseous phase growth of graphene.
The present invention provides the new method that a kind of ultra low temperature grows graphene.
The content of the invention
For the problems of the prior art, it is contemplated that inventing the new method that graphene is grown under a kind of ultra low temperature.
The invention provides a kind of method of low-temperature epitaxy graphene, comprise the following steps：
1）With crystalloid sodium chloride（NaCl）For substrate, used in advance thereon magnetically controlled sputter method pre-deposition a layer thickness for
10nm Zn films；
2）The NaCl substrates that above-mentioned pre-deposition there are Zn films are placed in tube type resistance furnace, 300-350 DEG C is heated to, is passed through H2-
CH4-N2 is reacting gas, and gas pressure intensity is 50-60Pa, wherein H2:CH4:N2 intrinsic standoff ratios are 25:60:15, react 3.5 hours；
3）After reaction terminates, power supply is closed, stopping is passed through N2 and CH4, continues to be passed through H2 gas, and rise to gas pressure intensity
1000Pa, using H2 air coolings, makes sample be quickly cooled to room temperature, obtains required product.
Present invention also offers a kind of graphene according to made from above-mentioned low-temperature growth method, the graphene is two-dimensional layer
Structure, thickness 2-5 nm, is grown on substrate vertically, and is interconnected to form loose structure, and hole is about 30-150nm, pattern
Even structure.
The useful achievement of the present invention is：
1）The method of the low-temperature epitaxy graphene of the present invention, uses NaCl for substrate, in one layer of Zn film of pre-deposition thereon, and
N2 is added in mixed gas, using interface mutual activation and coordinate catalytic action, and N2 gases are in the absorption on surface and auxiliary
Co-catalysis effect, can make growth temperature be reduced to 300 DEG C, and this is the low-down temperature of graphene growth, be also the present invention's
Main advantage.
2）The method of the low-temperature epitaxy graphene of the present invention, prepared graphene appearance structure is homogeneous, with porous knot
Structure, structural behaviour is excellent, can be applied in numerous areas such as lithium ion battery, ultracapacitor, catalysis, photoelectricity.
3）The method of the low-temperature epitaxy graphene of the present invention, the temperature of graphene can be grown by considerably reducing, and
High yield rate, equipment is simple, easy to operate, it is easy to promote, and industrialization production can be achieved.
Brief description of the drawings
Fig. 1 is the SEM for the low-temperature epitaxy grapheme material that embodiment 1 is obtained（SEM）Figure.
Embodiment
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
1）With crystalloid sodium chloride（NaCl）For substrate, used in advance thereon magnetically controlled sputter method pre-deposition a layer thickness for
10nm Zn films；
2）The NaCl substrates that above-mentioned pre-deposition there are Zn films are placed in tube type resistance furnace, 300 DEG C is heated to, is passed through H2-CH4-N2
For reacting gas, gas pressure intensity is 55Pa, wherein H2:CH4:N2 intrinsic standoff ratios are 25:60:15, react 3.5 hours；
3）After reaction terminates, power supply is closed, stopping is passed through N2 and CH4, continues to be passed through H2 gas, and rise to gas pressure intensity
1000Pa, using H2 air coolings, makes sample be quickly cooled to room temperature, obtains required product.
Embodiment 2
1）With crystalloid sodium chloride（NaCl）For substrate, used in advance thereon magnetically controlled sputter method pre-deposition a layer thickness for
10nm Zn films；
2）The NaCl substrates that above-mentioned pre-deposition there are Zn films are placed in tube type resistance furnace, 350 DEG C is heated to, is passed through H2-CH4-N2
For reacting gas, gas pressure intensity is 50Pa, wherein H2:CH4:N2 intrinsic standoff ratios are 25:60:15, react 3.5 hours；
3）After reaction terminates, power supply is closed, stopping is passed through N2 and CH4, continues to be passed through H2 gas, and rise to gas pressure intensity
1000Pa, using H2 air coolings, makes sample be quickly cooled to room temperature, obtains required product.
Embodiment 3
1）With crystalloid sodium chloride（NaCl）For substrate, used in advance thereon magnetically controlled sputter method pre-deposition a layer thickness for
10nm Zn films；
2）The NaCl substrates that above-mentioned pre-deposition there are Zn films are placed in tube type resistance furnace, 300 DEG C is heated to, is passed through H2-CH4-N2
For reacting gas, gas pressure intensity is 60Pa, wherein H2:CH4:N2 intrinsic standoff ratios are 25:60:15, react 3.5 hours；
3）After reaction terminates, power supply is closed, stopping is passed through N2 and CH4, continues to be passed through H2 gas, and rise to gas pressure intensity
1000Pa, using H2 air coolings, makes sample be quickly cooled to room temperature, obtains required product.
Microscopic appearance observation is carried out to final product graphene made from each embodiment using SEM, such as schemed
1 is the SEM for the low-temperature epitaxy grapheme material that embodiment 1 is obtained（SEM）Figure.Grown stone is shown in figure
Black alkene is two-dimensional layered structure, and thickness 2-5 nm are grown on substrate vertically, and are interconnected to form loose structure, and hole is about
For 30-150nm, appearance structure is uniform.Additional embodiment 2 or embodiment 3 grow obtained graphene microscopic appearance and embodiment 1
It is similar.
A kind of method of low-temperature epitaxy graphene of the present invention, uses NaCl for substrate, in one layer of Zn film of pre-deposition thereon,
And N2 is added in mixed gas, using the mutual activation and coordination catalytic action at interface, and N2 gases are in the absorption on surface
With auxiliary catalysis effect, growth temperature can be made to be reduced to 300 DEG C, this is the low-down temperature of graphene growth, is also this hair
Bright key.
It is described above, it will only be presently preferred embodiments of the present invention, any formal limitation not is made to the present invention.
Any those skilled in the art, without departing from the scope of the technical proposal of the invention, all using the disclosure above
Methods and techniques content makes many possible variations and modification to technical solution of the present invention, or is revised as the equivalent of equivalent variations
Embodiment.Therefore, every content without departing from technical scheme, the technical spirit according to the present invention is to above example
Any simple modifications, equivalents, and modifications done, still fall within technical solution of the present invention protection in the range of.
Claims (5)
1. a kind of method of low-temperature epitaxy graphene, it is characterised in that comprise the following steps：
1）Using crystalloid sodium chloride as substrate, magnetically controlled sputter method one layer of Zn film of pre-deposition is being used in advance thereon；
2）The sodium chloride substrate that above-mentioned pre-deposition there are Zn films is placed in tube type resistance furnace, 300-350 DEG C is heated to, is passed through H2-
CH4-N2 is reacting gas, is reacted 3.5 hours；
3）After reaction terminates, power supply is closed, stopping is passed through N2 and CH4, continues to be passed through H2 gas, and rise to gas pressure intensity
1000Pa, using H2 air coolings, makes sample be quickly cooled to room temperature, obtains required product graphene.
2. a kind of method of low-temperature epitaxy graphene according to claim 1, it is characterised in that：Step 2）It is passed through gas
Pressure is 50-60Pa.
3. a kind of method of low-temperature epitaxy graphene according to claim 1, it is characterised in that：Step 2）The reaction being passed through
Gas H2-CH4-N2, each gas H2:CH4:N2 intrinsic standoff ratios are 25:60:15.
4. a kind of method of low-temperature epitaxy graphene according to claim 1, it is characterised in that：Step 1）Middle pre-deposition one
The thickness of layer Zn films is 10nm.
5. the graphene prepared according to any one of Claims 1-4 low-temperature growth method, it is characterised in that：The graphite
Alkene is two-dimensional layered structure, and thickness 2-5 nm are grown on substrate vertically, and are interconnected to form loose structure, and hole is about
30-150nm, appearance structure is uniform.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757043A (en) * | 2012-08-10 | 2012-10-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing oriented graphene nanoribbon (GNR) array |
| TW201337029A (en) * | 2012-03-14 | 2013-09-16 | Nat Univ Tsing Hua | Chemical vapor deposition of graphene on dielectrics |
| CN103935982A (en) * | 2013-01-18 | 2014-07-23 | 海洋王照明科技股份有限公司 | Graphene nanoribbon preparation method |
| CN105067586A (en) * | 2015-08-12 | 2015-11-18 | 天津大学 | Nitrogen-doped three-dimensional graphene loaded carbon coated copper substrate material and preparation method |
-
2017
- 2017-06-29 CN CN201710517063.8A patent/CN107161985A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201337029A (en) * | 2012-03-14 | 2013-09-16 | Nat Univ Tsing Hua | Chemical vapor deposition of graphene on dielectrics |
| CN102757043A (en) * | 2012-08-10 | 2012-10-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing oriented graphene nanoribbon (GNR) array |
| CN103935982A (en) * | 2013-01-18 | 2014-07-23 | 海洋王照明科技股份有限公司 | Graphene nanoribbon preparation method |
| CN105067586A (en) * | 2015-08-12 | 2015-11-18 | 天津大学 | Nitrogen-doped three-dimensional graphene loaded carbon coated copper substrate material and preparation method |
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