CN107858663B - A method of using CVD method directly in Copper Powder Surface coated graphite alkene - Google Patents
A method of using CVD method directly in Copper Powder Surface coated graphite alkene Download PDFInfo
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- CN107858663B CN107858663B CN201711125991.6A CN201711125991A CN107858663B CN 107858663 B CN107858663 B CN 107858663B CN 201711125991 A CN201711125991 A CN 201711125991A CN 107858663 B CN107858663 B CN 107858663B
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- copper powder
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate
Abstract
The present invention propose it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, include the following steps: (1) p type single crystal silicon upper surface be deposited catalyst layer；(2) carbon nano tube growth is carried out；(3) copper powder is placed on carbon nano pipe array surface；(4) annealing 5min removes oxide on surface and copper crystal grain is made to grow up；(5) graphene growth is carried out, the copper powder of graphene package is obtained.The advantage of the invention is that copper powder is placed on carbon nano pipe array using Van der Waals force, preventing copper powder is not in large area sintering while being blown off.And can guarantee that copper powder is completely covered by few layer of graphene using gaseous carbon sources and increase its antioxygenic property, its electric conductivity is also ensured while improving its oxidation resistance in air using the copper powder that this method prepares graphene package.
Description
Technical field
The present invention relates to a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, in particular to
A kind of Copper Powder Surface method fully wrapped around by graphene.
Background technique
Copper is a kind of electric conductivity and all preferable metal material of thermal conductivity, is used in the industry such as electrical, mechanical.Copper at present
Powder especially copper nanoparticle is widely used in the fields such as conductive material, high-energy catalyst because of its unique performance.In addition,
Since the price of copper powder is much lower compared to inert metals such as gold, silver, so that it starts to be concerned.But naked copper powder is especially
It is that naked copper nanoparticle will soon be oxidized to cuprous oxide or copper oxide in the environment of room temperature.Therefore to enable copper powder
It is enough widely used and has to solve the problems, such as that it is easily oxidized.It is a kind of ideal material that Copper Powder Surface, which wraps up graphene, can
Slow down the speed that it is oxidized while keeping its electric conductivity.In copper powder anti-oxidant treatment, silane coupling agent wraps up the side of copper powder
Method can reduce its electric conductivity；Or the graphene grown is transferred to Copper Powder Surface, graphene and Copper Powder Surface cannot be very
It contacts well and will affect its conductive and heating conduction.And graphene is directly grown in Copper Powder Surface and not only solves the problems, such as that its is anti-oxidant
And it not will be greatly reduced its electric conductivity and thermal conductivity.
Graphene is a kind of novel material, because its unique nano-meter characteristic is widely used in heat dissipation, conduction etc.,
It has high-termal conductivity, high chemical stability, since graphene is found, it realized as added material high-termal conductivity,
The research of high mechanical strength etc. is concerned, but the research phase for directly growing graphene in Copper Powder Surface and being applied
To less.
He Yuehui seminar, Central South University utilizes metallo-organic compound chemical gas at 600 DEG C of horizontal stove dual temperature area for the first time
Phase deposition process obtain multi-layer graphene package copper nanoparticle, at room temperature exposure in air 60 days its obviously do not aoxidized.
Zhao Naiqin seminar, University Of Tianjin is mutually tied using PMMA as solid carbon source by ball milling and CVD thermal anneal process
The method of conjunction obtains Copper Powder Surface wrapped multiple graphene.From initial PMMA powder to PMMA liquid so that Copper Powder Surface is abundant
By graphene coated, copper and the compound material of graphene is successfully made, has improved its yield strength and tensile strength.
Switzerland Norman A Luchinger et al. is using the method for reproducibility flame in Copper Powder Surface growth in situ graphite
Alkene makes it have chemical inertness and stability, and then the copper powder that graphene wraps up is made to the ink of ink jet printing, obtain conduction
Property be greater than 1S/cm circuit, furthermore the printed circuit have high chemical stability.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.
For this purpose, an object of the present invention is to provide a kind of using CVD method directly in Copper Powder Surface coated graphite alkene
Method.
It is according to an embodiment of the present invention it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, including
Following steps:
(1) using electron beam evaporation deposition machine on the p type single crystal silicon with one layer of 200nm silica of 350 μ m-thicks
Catalyst layer is deposited in surface；
(2) using CVD in the 3min that anneals at 550 DEG C, carbon nano tube growth 4min is then carried out at 665 DEG C；
(3) copper powder is placed on to the carbon nano pipe array surface of step (2) acquisition, so that copper powder is adsorbed on carbon by vibration and receives
Then nanotube surface removes extra copper powder；
(4) copper powder in step (3) is put into vertical cold wall CVD with carbon nanotube, be passed through at 775 DEG C hydrogen and
Argon annealed 5min removes oxide on surface and copper crystal grain is made to grow up in order to graphene growth；
(5) methane, hydrogen and argon gas then are passed through at 775 DEG C, wherein methane carries out graphene life as gaseous carbon sources
Long, growth time 5min, hydrogen is reducibility gas, and argon gas is protective gas, last to be first down to 300 with 200 DEG C/min
DEG C, be then down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene package copper powder.
Advantageously, in step (1), catalyst layer is the aluminium oxide of 20nm and the iron of 1nm
Advantageously, in step (2), reducing gas is the hydrogen of flow velocity 700sccm, and carbon-source gas is flow velocity 100sccm's
Acetylene.
Advantageously, in step (3), copper powder is the copper nanoparticle that surface is covered with sodium citrate dispersing agent.
Advantageously, the size of the copper powder is 15nm to 700nm.
Advantageously, in step (4), hydrogen flowing quantity 30sccm, argon flow 1000sccm.
Advantageously, in step (5), methane flow rate 10sccm, hydrogen flow rate 30sccm, argon gas flow velocity is
1000sccm。
It is according to an embodiment of the present invention it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, for the first time
Copper powder is uniformly distributed on the carbon nanotubes, then directly utilizes gaseous carbon sources growth in situ uniform using vertical cold wall CVD
Few layer of graphene wrap up copper powder.
The advantage of the invention is that copper powder is placed on carbon nano pipe array using Van der Waals force, prevent copper powder from being blown off
While be not in large area sintering.And it can guarantee that copper powder completely covers increase by few layer of graphene using gaseous carbon sources
Its antioxygenic property prepares the copper powder of graphene package while improving its oxidation resistance in air using this method
It ensure that its electric conductivity.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the SEM figure of the copper powder of sodium citrate dispersing agent package
Fig. 2 is the SEM figure of Copper Powder Surface package graphene after CVD growth
Fig. 3 a and Fig. 3 b are the partial enlargement SEM figure of Copper Powder Surface package graphene after CVD growth
Fig. 4 is the Raman figure that Copper Powder Surface wraps up graphene
Fig. 5 is that Copper Powder Surface wraps up the XRD diagram after exposing 90 days in graphene air
Fig. 6 pure copper powder is placed on silica surface and carries out the SEM figure after graphene growth
Fig. 7 pure copper powder is placed on silica surface and carries out the partial enlargement SEM figure after graphene growth
Specific embodiment
Embodiment 1
(1) using electron beam evaporation deposition machine on the p type single crystal silicon with one layer of 200nm silica of 350 μ m-thicks
Catalyst layer is deposited in surface, which is the aluminium oxide of 20nm and the iron of 1nm；
(2) using CVD in the 3min that anneals at 550 DEG C, carbon nano tube growth 4min is then carried out at 665 DEG C, wherein
Reducing gas is hydrogen, and flow velocity 700sccm, carbon-source gas is acetylene, flow velocity 100sccm
(3) copper powder is placed on carbon nano pipe array surface, so that copper powder is adsorbed on carbon nano tube surface by vibration, then
Remove extra copper powder
(4) copper powder in step (3) is put into vertical cold wall CVD, is passed through hydrogen and argon annealed at 775 DEG C
5min removes oxide on surface and copper crystal grain is made to grow up in order to graphene growth, is then passed through methane as gas at 775 DEG C
Carbon source carries out graphene growth, and growth time 5min, wherein methane flow rate is 10sccm, last to be first down to 200 DEG C/min
300 DEG C, be then down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene package copper
Powder, hydrogen flow rate 30sccm, argon gas flow velocity is 1000sccm, as shown in Fig. 2, its partial enlarged view is as shown in Figure 3.
(5) phenetic analysis then is carried out to obtained copper powder, shows that few layer graphene exists by the test of Fig. 4 Raman, figure
The presence of 5XRD test surfaces graphene and simple substance copper crystal, while exposure in 90 days is with the presence of some cuprous oxide.
Comparative example
Copper powder is directly placed at silicon oxide surface and puts CVD furnace into using the identical graphene conditioned growth of example 1, copper powder
Surface is wrapped up by graphene, as shown in Figure 6.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are within the scope of the invention to above-mentioned implementation
Example be changed, modify, replacement and variant, each fall within protection scope of the present invention.
Claims (1)
1. it is a kind of using CVD method directly in the method for Copper Powder Surface coated graphite alkene, which comprises the steps of:
(1) using electron beam evaporation deposition machine in the p type single crystal silicon upper surface with one layer of 200nm silica of 350 μ m-thicks
Catalyst layer is deposited, wherein the catalyst layer is the aluminium oxide of 20nm and the iron of 1nm；
(2) it is annealed at 550 DEG C 3min using CVD, carbon nano tube growth 4min is then carried out at 665 DEG C, wherein also Primordial Qi
Body is the hydrogen of flow velocity 700sccm, and carbon-source gas is the acetylene of flow velocity 100sccm；
(3) copper powder is placed on to the carbon nano pipe array surface of step (2) acquisition, so that copper powder is adsorbed on carbon nanotube by vibration
Then surface removes extra copper powder, wherein the copper powder is the copper nanoparticle that surface is covered with sodium citrate dispersing agent, described
The size of copper powder is 15nm to 700nm；
(4) copper powder in step (3) is put into vertical cold wall CVD with carbon nanotube, is passed through hydrogen and argon gas at 775 DEG C
Annealing 5min removes oxide on surface and copper crystal grain is made to grow up in order to graphene growth, wherein hydrogen flowing quantity 30sccm, argon
Throughput is 1000sccm；
(5) methane, hydrogen and argon gas then are passed through at 775 DEG C, wherein methane carries out graphene growth as gaseous carbon sources, raw
It is for a long time 5min, hydrogen is reducibility gas, and argon gas is protective gas, it is last to be first down to 300 DEG C with 200 DEG C/min, it connects
Be down in the air-flow of hydrogen and argon gas 150 DEG C be then turned on air pump close gas obtain graphene package copper powder, wherein institute
Stating methane flow rate is 10sccm, and hydrogen flow rate 30sccm, argon gas flow velocity is 1000sccm.
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| CN110666159B (en) * | 2019-09-30 | 2022-04-01 | 元颉新材料科技(浙江)有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN113981410B (en) * | 2021-10-26 | 2023-12-15 | 化学与精细化工广东省实验室潮州分中心 | Antioxidant super-hydrophobic copper film and preparation method thereof |
| CN114854200B (en) * | 2022-05-17 | 2023-04-18 | 广东墨睿科技有限公司 | Preparation method of high-thermal-conductivity graphene composite thermal-conductivity grease |
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| CN104053827A (en) * | 2011-12-09 | 2014-09-17 | 贝克休斯公司 | Method of forming carbonaceous particles and articles therefrom |
| CN106191805A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene laminated film |
| CN106191804A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene nano belt/graphene composite film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104053827A (en) * | 2011-12-09 | 2014-09-17 | 贝克休斯公司 | Method of forming carbonaceous particles and articles therefrom |
| CN106191805A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene laminated film |
| CN106191804A (en) * | 2016-06-06 | 2016-12-07 | 重庆大学 | A kind of preparation method of magnetic graphene nano belt/graphene composite film |
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