CN109402605A - A kind of preparation method of the graphene that the large area number of plies is controllable and hexagonal boron nitride hetero-junctions - Google Patents
A kind of preparation method of the graphene that the large area number of plies is controllable and hexagonal boron nitride hetero-junctions Download PDFInfo
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- CN109402605A CN109402605A CN201811358576.XA CN201811358576A CN109402605A CN 109402605 A CN109402605 A CN 109402605A CN 201811358576 A CN201811358576 A CN 201811358576A CN 109402605 A CN109402605 A CN 109402605A
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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
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- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
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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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- 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
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Abstract
The present invention provides a kind of method for preparing the number of plies controllable graphene and hexagonal boron nitride hetero-junctions, include: that hexagonal boron nitride is prepared in metallic film substrate surface by chemical vapour deposition technique under the catalysis of metallic film substrate, graphene is formed on the hexagonal boron nitride surface prepared by chemical vapour deposition technique under the long-range catalysis for another metal material that air-flow upstream end is placed.The metal material is compared with the metallic film substrate material with higher boron nitrogen solubility or with the metal material of high specific surface area.It is placed around metal material in growth substrates in preparation method of the present invention, the hetero-junctions of the large area number of plies controllable graphene and hexagonal boron nitride can be prepared in situ out.Metal substrate surface is first by after the hexagonal boron nitride covering of certain number of plies, and after losing chemical catalysis activity, surface can not continue catalytic growth graphene.The metal material being pre-placed at this time can continue to provide catalysis, to grow graphene on hexagonal boron nitride surface.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of graphene that the large area number of plies is controllable and hexagonal boron nitride are heterogeneous
The preparation method of knot.
Background technique
Graphene is the two dimensional crystal with regular six side's symmetrical structures by single layer of carbon atom by Covalent bonding together, is
The thickness being currently known is most thin, the maximum two-dimensional material of hardness, light, electricity, heat, power, sound, in terms of have and widely answer
Use prospect.The hetero-junctions of graphene and hexagonal boron nitride can show many peculiar and excellent physical properties, especially when
When hexagonal boron nitride is multilayer, the carrier mobility of graphene can be greatlyd improve, for high-efficient graphite alkene electricity device
Using laying fabulous basis.Current multilayer hexagonal boron nitride and graphene hetero-junctions is mostly mechanical stripping method and wet chemical
Transfer is prepared, these methods not only low output but also can generate more impurity during the preparation process, is unfavorable for industry metaplasia
It produces.The current existing technology that hexagonal boron nitride and graphene hetero-junctions are prepared in situ using chemical vapor deposition, often can only
Prepare the hetero-junctions of single layer hexagonal boron nitride.For this purpose, needing development one-step method is prepared in situ controllable thickness graphene and multilayer six
The technology of square boron nitride hetero-junctions realizes two-dimensional material LBL self assembly.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the number of plies controllable graphene and hexagonal boron nitride hetero-junctions, with
Existing method is compared, and preparation method of the present invention is simple and effective, can obtain clean heterojunction boundary.
The method of the preparation number of plies provided by the present invention controllable graphene and hexagonal boron nitride hetero-junctions, including walk as follows
It is rapid: hexagonal boron nitride is prepared in metallic film substrate surface by chemical vapour deposition technique under the catalysis of metallic film substrate,
The lower chemical vapour deposition technique that passes through of the long-range catalysis for another metal material that air-flow upstream end is placed is in the six sides nitridation prepared
Boron surface forms graphene, to realize being prepared in situ for graphene and hexagonal boron nitride hetero-junctions.
The method specifically includes operations described below:
Another metal material II is placed near metallic film substrate I and in air-flow upstream end, by boracic nitrogen compound
It is introduced into reaction chamber as boron nitrogen source, prepares six by chemical vapour deposition reaction on the surface metallic film substrate I
Square boron nitride stops introducing boron nitrogen source, introduce containing carbon compound as carbon source, so that carbon source is in another metal material II
Long-range catalysis it is lower generate carbon atom, graphite is formed on the hexagonal boron nitride surface prepared by chemical vapour deposition reaction
Alkene, to realize being prepared in situ for graphene and hexagonal boron nitride hetero-junctions.
In the above method, the material that the metallic film substrate I is used can be transition metal or aluminium (Al), magnesium (Mg), institute
Stating transition metal can be selected from copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), chromium (Cr), manganese (Mn), molybdenum
(Mo), one of ruthenium (Ru), tantalum (Ta), titanium (Ti), rhodium (Rh) and tungsten (W) or any two or more combination, concretely
Copper.
Another metal material II be comparably with the metallic film substrate I material with higher boron nitrogen solubility or
Metal material with high specific surface area, can for aluminium, magnesium, nickel, copper, cobalt, iron, platinum, gold, chromium, manganese, molybdenum, ruthenium, titanium, rhodium, tungsten,
At least one of with tantalum, or any two or more combination, it include its alloy combination.
Specifically, when the material that the metallic film substrate I is used is copper, another metal material II can for aluminium,
One kind or any two or more combination of magnesium, nickel, copper, iron, cobalt, platinum, chromium, manganese, titanium, rhodium, tungsten and tantalum.
The form of another metal material II is unlimited, can be block, film, perforated foams, nanometer powder etc..
When the metallic film substrate I material is Copper thin film, another metal material II can be foam copper, nickel foam
Or the material forms that the specific surface areas such as cobalt nano powder are bigger than film.
The boracic nitrogen compound as boron nitrogen source can be the mixing of ammonia borine, borazine, diborane and ammonia
The mixture of object or halogenation boron and ammonia.
Wherein, the halogenation boron can be at least one of boron chloride, boron fluoride or boron bromide.
In the above method, the number of plies of prepared hexagonal boron nitride can be regulated and controled by changing the flux of boron nitrogen source.
The carbon compound that contains as carbon source includes at least one of alkane, alkene, alkynes and aromatic hydrocarbon.
Wherein, the alkane includes at least one of methane, ethane, propane and butane；
The alkene includes at least one of ethylene, propylene and butylene；
The alkynes is acetylene and/or propine；
The aromatic hydrocarbon is naphthalene and/or coronene.
In the above method, the controllable of graphene number of plies can be realized with the time for being passed through carbon source by the flow for changing carbon source
It is standby.
In the above method, carrier gas can be used, gaseous boron nitrogen source, carbon source are introduced into reaction chamber, the carrier gas can be hydrogen
Gas, argon gas or nitrogen；
The flow velocity of the carrier gas can be 1sccm~1000sccm, concretely 8sccm；
When the boron nitrogen source is solid-state, six prepared side's nitrogen can be regulated and controled by adjusting the decomposition temperature of solid-state boron nitrogen source
Change boron layer number.
When the boron nitrogen source is gaseous state, flow can be 1~1000sccm, specifically to need hexagonal boron to be prepared
Subject to number.
When the carbon source is solid-state, the graphene layer of preparation needed for being regulated and controled by adjusting the decomposition temperature of solid-state carbon source
Number；
When the carbon source is gaseous state, flow velocity can be 1~1000sccm, specifically be with the graphene number of plies that needs are prepared
It is quasi-.
In the above method, when carrying out the chemical vapour deposition reaction, system pressure can be 10Pa~105Pa specifically may be used
For 16Pa；
The temperature of the chemical vapour deposition reaction can be 800 DEG C~1100 DEG C, concretely 1030 DEG C；
The time of the chemical vapour deposition reaction can be 1min~200min concretely 30min.
The above method further includes that the temperature of reaction system is down to room temperature after carrying out the chemical vapour deposition reaction
The step of；
Time by greenhouse cooling to the room temperature of the chemical vapour deposition reaction is 5min~60min, concretely
20min。
In the above method, the method also includes carrying out for the first time before chemical vapour deposition reaction by the metallic film
The step of substrate I and metal material II are annealed；
The temperature of the annealing can be 800 DEG C~1500 DEG C, concretely 1050 DEG C；
The time of the annealing can be 5min~75min, concretely 30min；
The time that the annealing temperature is risen to by room temperature can be 10~60min, concretely 30min.
In the present invention, the room temperature refers to common sense well known in the art, is 10~30 DEG C.
Graphene prepared by the above method and hexagonal boron nitride hetero-junctions also belong to protection scope of the present invention.
The invention has the following advantages that
It is placed around another metal material in growth substrates in preparation method of the present invention, the large area number of plies can be prepared in situ out
The hetero-junctions of controllable graphene and hexagonal boron nitride.After metal substrate surface is first covered by the hexagonal boron nitride of certain number of plies,
After losing chemical catalysis activity, surface can not continue catalytic growth graphene.Another metal material being pre-placed at this time, by
In its higher boron or nitrogen solubility or specific surface area with higher, can continue to provide catalytic action, thus in six side's nitrogen
Change boron surface and grows graphene.
Detailed description of the invention
Fig. 1 shows the positional relationships of metallic film substrate and another metal material.1 is metallic film substrate, and 2 be to provide volume
The metal material of outer catalysis.
Fig. 2 is the principle of the present invention schematic diagram, grows the hexagonal boron nitride of certain number of plies on metallic film substrate 1 first
3, the mode of growth is chemical vapor deposition；After growing the hexagonal boron nitride 3 of certain number of plies on metallic film substrate 1, gold
Belong to film-substrate 1 and loses chemical catalysis activity, and the metal material 2 with higher boron nitrogen solubility or with high specific surface area
Continue catalytic hydrocarbon and decompose generation carbon, graphene 4 is grown on hexagonal boron nitride 3.
Fig. 3 is the scanning electron microscope (SEM) of graphene prepared by the embodiment of the present invention 1 and hexagonal boron nitride hetero-junctions
The high component of transmission electron microscope (HRTEM) of photo and the double-deck hexagonal boron nitride.
Fig. 4 is Raman (Raman) data of graphene prepared by the embodiment of the present invention 1 and hexagonal boron nitride hetero-junctions.
Fig. 5 is the hexagonal boron nitride region of graphene prepared by the embodiment of the present invention 1 and multilayer hexagonal boron nitride hetero-junctions
Atomic force microscope (AFM) figure.
Fig. 6 is x-ray photoelectron spectroscopy (XPS) data of graphene prepared by the embodiment of the present invention 2 and hexagonal boron nitride.
Fig. 7 is the graphene of different thickness prepared by the embodiment of the present invention 2 and the SEM photograph of hexagonal boron nitride.
Fig. 8 is the embodiment of the present invention 3 using copper foil as growth substrates, uses copper sheet and foam copper as auxiliary catalysis metal respectively
Preparation result.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1, the method for preparing graphene Yu hexagonal boron nitride hetero-junctions using nickel foam and copper foil substrate
According to principle in Fig. 1-Fig. 2, the method for preparing graphene Yu hexagonal boron nitride hetero-junctions specifically includes following step
It is rapid:
(1) by nickel foam, (concrete specification, with a thickness of 3mm, aperture 0.1mm, per inch hole count is 100) and copper foil is (thick
25 microns of degree, size 3cm*4cm) it is impregnated 2-3 minutes with ammonium persulfate solution, to remove the oxide on surface, then spend
Ionized water cleaning.
(2) copper foil is bundled into box-like, nickel foam is cut into one end that 2cm*2cm is packed in copper (substrate) box, then uses day
The flat ammonia borine 20mg that weighs is put into quartz boat as growth raw material.The quartz boat of raw material will be filled together with copper box
It is put into tube furnace, wherein copper box is located at the middle position (reaction zone) of high-temperature region, and is placed in gas for one section that is packed in nickel foam
Upstream end is flowed, quartz boat is placed on source region position, closed system.
(3) it is passed through the hydrogen of 8sccm in tubular type furnace system, and is warming up in 30 minutes by room temperature (15-25 DEG C)
1030 DEG C, and in same atmosphere, it is kept for 1030 DEG C, annealed 30 minutes to growth substrates, to increase the crystal grain of copper foil
Size facilitates the growth of hetero-junctions.
(4) after the completion of annealing, the temperature of reaction zone is continually maintained in 1030 DEG C, in the case where keeping hydrogen flowing quantity constant,
To source region temperature is heated to 100 DEG C by room temperature simultaneously, hydrogen will decompose the boron-nitrogen compound generated bring to reaction zone start into
Row hexagonal boron nitride chemical vapor deposition.
(5) depositing temperature is 1030 DEG C, time 30min, stops heating source region later, and by source region in 1 minute
Temperature is cooled to room temperature.
(6) it keeps hydrogen flowing quantity constant, is passed through the methane of 3sccm 10 minutes, carries out the chemical vapor deposition of graphene.
(7) it keeps atmosphere constant, tube furnace power supply is closed, in reaction zone temperature is down to room temperature in ten minutes.
(8) the hetero-junctions sample prepared then is transferred to SiO2On/Si substrate, and use scanning electron microscope
(SEM) shooting photo is as shown in Figure 3a, and what can be prepared by the determination of apparent contrast difference is graphene and hexagonal boron nitride
Hetero-junctions.The sample shifted is characterized using Raman spectrometer (Raman), as a result as shown in figure 4, being believed by Raman signatures
What is prepared known to number is the hetero-junctions of graphene and hexagonal boron nitride.And G peak intensity (I in the Raman signal of grapheneG) and
2D peak intensity (I2D) ratio (IG/I2D) it is 1/2, single-layer graphene can be confirmed as.The number of plies of hexagonal boron nitride can be by that will prepare
Good sample is transferred on transmission electron microscope copper mesh, and is confirmed as bilayer by HRTEM (Fig. 3 b).
(9) as described in the embodiment, can be when depositing hexagonal boron nitride, by changing source region temperature to 130 DEG C, Bian Ke
The hexagonal boron nitride (Fig. 5) that thickness reaches 3.45nm is prepared on substrate.
Embodiment 2, the method for preparing graphene Yu hexagonal boron nitride hetero-junctions using cobalt nano powder and copper foil substrate
(1) copper foil is impregnated 2-3 minutes with (25 microns of thickness, size 3cm*4cm) with ammonium persulfate solution, to remove table
The oxide in face, is then cleaned with deionized water.
(2) weigh with scale 3mg cobalt nano powder (2nm) for use, copper foil is then bundled into box-like, before sealing, will be claimed
Measured nano powder is uniformly sprinkling upon the fold position of copper box.Then ammonium borine 20mg is weighed with scale as growth raw material, and
It is put into quartz boat.The quartz boat for filling raw material and copper box are put into togerther tube furnace, wherein copper box is located at high-temperature region
Middle position, and the fold position for being placed with cobalt nano powder is placed in air-flow upstream end, and quartz boat is placed on source region position, closing system
System.
(3) it is passed through the hydrogen of 8sccm in tubular type furnace system, and is warming up in 30 minutes by room temperature (15-25 DEG C)
1030 DEG C, and in same atmosphere, it is kept for 1030 DEG C, annealed 30 minutes to growth substrates, to increase the crystal grain of copper foil
Size facilitates the growth of hetero-junctions.
(4) after the completion of annealing, the temperature of reaction zone is continually maintained in 1030 DEG C, in the case where keeping hydrogen flowing quantity constant,
To source region temperature is heated to 100 DEG C by room temperature simultaneously, hydrogen will decompose the boron-nitrogen compound generated bring to reaction zone start into
Row hexagonal boron nitride chemical vapor deposition.
(5) depositing temperature is 1030 DEG C, time 30min, stops heating source region later, and by source region in 1 minute
Temperature is cooled to room temperature.
(6) it keeps hydrogen flowing quantity constant, is passed through the methane of 5sccm 10 minutes, carries out the chemical vapor deposition of graphene.
(7) it keeps atmosphere constant, tube furnace power supply is closed, in reaction zone temperature is down to room temperature in 20 minutes.
(8) the hetero-junctions sample prepared then is transferred to SiO2On/Si substrate, and carry out photoelectron spectroscopy (Fig. 6)
Measurement, is further determined that by XPS peak position and successfully prepares hetero-junctions.
(9) as described in the embodiment, it when depositing graphene, by changing methane flow, can be prepared on boron nitride
Single layer (5sccm methane), double-deck (3sccm methane) and three layers of (1sccm methane) graphene (Fig. 7).
Embodiment 3, using copper sheet and foam copper respectively as the comparative experiments of additional metal catalysis material
(1) by preceding embodiment processing copper sheet (with a thickness of 50 μm, size 2cm*2cm), foam copper (concrete specification, thickness
For 3mm, aperture 0.1mm, per inch hole count is 100, size 2cm*2cm) and two panels copper foil (25 μm of thickness, size is
3cm*4cm)；
(2) two panels copper foil is bundled into box-like, the foam copper handled well and copper sheet is packed in copper (substrate) box one end, so
After weigh with scale ammonia borine 20mg as growth raw material, and be put into quartz boat.The quartz boat and copper box of raw material will be filled
Son is put into togerther tube furnace, and wherein copper box is located at the middle position (reaction zone) of high-temperature region, and will be packed in foam copper and copper sheet
One section be placed in air-flow upstream end, in addition to keep growth conditions consistent, two copper boxes place (such as Fig. 8 a) side by side, quartzy
Boat is placed on source region position, closed system.
(3) it is passed through the hydrogen of 8sccm in tubular type furnace system, and is warming up in 30 minutes by room temperature (15-25 DEG C)
1030 DEG C, and in same atmosphere, it is kept for 1030 DEG C, annealed 30 minutes to growth substrates, to increase the crystal grain of copper foil
Size facilitates the growth of hetero-junctions.
(4) after the completion of annealing, the temperature of reaction zone is continually maintained in 1030 DEG C, in the case where keeping hydrogen flowing quantity constant,
To source region temperature is heated to 75 DEG C by room temperature simultaneously, hydrogen will decompose the boron-nitrogen compound generated and bring to be started to carry out to reaction zone
Hexagonal boron nitride chemical vapor deposition.
(5) depositing temperature is 1030 DEG C, time 30min, stops heating source region later, and by source region in 1 minute
Temperature is cooled to room temperature.
(6) it keeps atmosphere constant, is passed through the methane of 1sccm, start to carry out graphene chemical vapor deposition, depositing temperature is
1030 DEG C, time 20min.After the completion of deposition, under conditions of keeping atmosphere constant, reaction zone temperature is down in 20 minutes
Room temperature.
(7) prepare two copper foil substrates are observed into its surface topography with SEM, as a result as shown in Fig. 8 b-c, is shone by SEM
Piece as it can be seen that copper sheet as additional catalytic object, since it neither has higher boron nitrogen solubility nor has biggish specific surface
Product, surface lose catalytic activity because covering full single layer hexagonal boron nitride film as the copper foil substrate of growth, therefore only
Single layer hexagonal boron nitride (Fig. 8 b) is obtained in copper foil surface, and foam copper has biggish specific surface area, therefore can continue to be catalyzed
Methane cracking can effectively prepare the hetero-junctions (Fig. 8 c) of graphene and boron nitride in brass bottom surface.
Claims (10)
1. a kind of method for preparing graphene Yu hexagonal boron nitride hetero-junctions, it is characterised in that: described method includes following steps:
Hexagonal boron nitride is prepared in metallic film substrate surface by chemical vapour deposition technique under the catalysis of metallic film substrate, in air-flow
The lower chemical vapour deposition technique that passes through of the long-range catalysis for another metal material that upstream end is placed is in the hexagonal boron nitride table prepared
Face forms graphene, to realize being prepared in situ for graphene and hexagonal boron nitride hetero-junctions.
2. according to the method described in claim 1, it is characterized by: the method includes operating as follows:
Place another metal material II near metallic film substrate I and in air-flow upstream end, using boracic nitrogen compound as
Boron nitrogen source is introduced into reaction chamber, prepares six side's nitrogen by chemical vapour deposition reaction on the surface metallic film substrate I
Change boron, stops introducing boron nitrogen source, introduce containing carbon compound as carbon source, so that carbon source is in the remote of another metal material II
Carbon atom is generated under Cheng Cuihua, graphene is formed on the hexagonal boron nitride surface prepared by chemical vapour deposition reaction,
To realize being prepared in situ for graphene and hexagonal boron nitride hetero-junctions.
3. according to the method described in claim 2, it is characterized by: the material that uses of the metallic film substrate is transition metal
Or aluminium, magnesium；
The transition metal is selected from one of copper, nickel, cobalt, iron, platinum, gold, chromium, manganese, molybdenum, ruthenium, tantalum, titanium, rhodium and tungsten or any
Two or more combinations.
4. according to the method in claim 2 or 3, it is characterised in that: another metal material II be and the metal foil
Film substrate I material is compared with higher boron nitrogen solubility or with the metal material of high specific surface area, specially aluminium, magnesium, nickel,
At least one of copper, cobalt, iron, platinum, gold, chromium, manganese, molybdenum, ruthenium, titanium, rhodium, tungsten and tantalum, or any two or more combination, packet
Containing its alloy combination.
5. the method according to any one of claim 2-4, it is characterised in that: the material that the metallic film substrate I is used
Material is copper, and another metal material II is one kind of aluminium, magnesium, nickel, copper, iron, cobalt, platinum, chromium, manganese, titanium, rhodium, tungsten and tantalum or appoints
It anticipates two or more combinations.
6. the method according to any one of claim 2-5, it is characterised in that: the change of the boracic nitrogen as boron nitrogen source
Conjunction object is the mixture of borazine, the mixture of diborane and ammonia or halogenation boron and ammonia；
Wherein, the halogenation boron is at least one of boron chloride, boron fluoride or boron bromide；
The carbon compound that contains as carbon source includes at least one of alkane, alkene, alkynes and aromatic hydrocarbon.
Wherein, the alkane includes at least one of methane, ethane, propane and butane；
The alkene includes at least one of ethylene, propylene and butylene；
The alkynes is acetylene and/or propine；
The aromatic hydrocarbon is naphthalene and/or coronene.
7. the method according to any one of claim 2-6, it is characterised in that: in the method, using carrier gas by gaseous state
Boron nitrogen source, carbon source be introduced into reaction chamber, the carrier gas be hydrogen, argon gas or nitrogen；
The flow velocity of the carrier gas is 1sccm~1000sccm.
8. the method according to any one of claim 2-7, it is characterised in that: the method also includes carrying out describedization
Learn the step of temperature of reaction system is down to room temperature later by vapor deposition reaction；
Time by greenhouse cooling to the room temperature of the chemical vapour deposition reaction is 5min~60min；
The method also includes carrying out for the first time before chemical vapour deposition reaction by the metallic film substrate and metal material
The step of being annealed；
The temperature of the annealing is 800 DEG C~1500 DEG C；
The time of the annealing is 5min~75min；
It is 10~60min by the time that room temperature rises to the annealing temperature.
9. the method according to any one of claim 2-8, it is characterised in that: in the method, carry out the chemical gas
When phase deposition reaction, system pressure is 10Pa~105Pa；
The temperature of the chemical vapour deposition reaction is 800 DEG C~1100 DEG C；
The time of the chemical vapour deposition reaction is 1min~200min.
10. the graphene and hexagonal boron nitride hetero-junctions that are prepared by any one of claim 1-9 the method.
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| CN113013020A (en) * | 2021-02-23 | 2021-06-22 | 中国人民大学 | Large-area ultrathin two-dimensional nitride growth method based on thickness etching |
| CN113053732A (en) * | 2021-03-15 | 2021-06-29 | 吉林大学 | High-quality hexagonal boron nitride film grown by taking diamond as substrate and preparation method thereof |
| CN113380603A (en) * | 2021-05-18 | 2021-09-10 | 厦门大学 | High-boron-component two-dimensional III-group multi-element nitride mixed crystal and preparation method thereof |
| CN115613162A (en) * | 2021-07-15 | 2023-01-17 | 北京石墨烯研究院 | Composite fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392226A (en) * | 2011-11-28 | 2012-03-28 | 无锡第六元素高科技发展有限公司 | Preparation method of grapheme/ boron nitride heterogeneous film |
| WO2017064113A1 (en) * | 2015-10-15 | 2017-04-20 | Basf Se | Metal free graphene synthesis on insulating or semiconducting substrates |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| CN107815664A (en) * | 2017-10-24 | 2018-03-20 | 中国科学技术大学 | Chemical vapor depsotition equipment, method and purposes |
| CN207418858U (en) * | 2017-10-24 | 2018-05-29 | 中国科学技术大学 | Chemical vapor depsotition equipment |
-
2018
- 2018-11-15 CN CN201811358576.XA patent/CN109402605A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392226A (en) * | 2011-11-28 | 2012-03-28 | 无锡第六元素高科技发展有限公司 | Preparation method of grapheme/ boron nitride heterogeneous film |
| WO2017064113A1 (en) * | 2015-10-15 | 2017-04-20 | Basf Se | Metal free graphene synthesis on insulating or semiconducting substrates |
| CN107244666A (en) * | 2017-05-31 | 2017-10-13 | 山东大学 | A kind of method using hexagonal boron nitride as the point big domain graphene of seeded growth |
| CN107815664A (en) * | 2017-10-24 | 2018-03-20 | 中国科学技术大学 | Chemical vapor depsotition equipment, method and purposes |
| CN207418858U (en) * | 2017-10-24 | 2018-05-29 | 中国科学技术大学 | Chemical vapor depsotition equipment |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113013020A (en) * | 2021-02-23 | 2021-06-22 | 中国人民大学 | Large-area ultrathin two-dimensional nitride growth method based on thickness etching |
| CN113013020B (en) * | 2021-02-23 | 2023-06-27 | 中国人民大学 | Growth method of large-area ultrathin two-dimensional nitride based on thickness etching |
| CN113053732A (en) * | 2021-03-15 | 2021-06-29 | 吉林大学 | High-quality hexagonal boron nitride film grown by taking diamond as substrate and preparation method thereof |
| CN113380603A (en) * | 2021-05-18 | 2021-09-10 | 厦门大学 | High-boron-component two-dimensional III-group multi-element nitride mixed crystal and preparation method thereof |
| CN115613162A (en) * | 2021-07-15 | 2023-01-17 | 北京石墨烯研究院 | Composite fiber and preparation method thereof |
| CN115613162B (en) * | 2021-07-15 | 2024-02-09 | 北京石墨烯研究院 | Composite fiber and preparation method thereof |
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