CN103979975B - A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material - Google Patents
A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material Download PDFInfo
- Publication number
- CN103979975B CN103979975B CN201410201072.2A CN201410201072A CN103979975B CN 103979975 B CN103979975 B CN 103979975B CN 201410201072 A CN201410201072 A CN 201410201072A CN 103979975 B CN103979975 B CN 103979975B
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- graphite
- multilamellar
- carbon nitrogen
- heterojunction structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to the synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material; the method specifically includes following steps: (1) is by high-purity hexagonal boron nitride and graphite (or Graphene) powder; under protective gas atmosphere; by certain mol proportion alternatively layered closed assembly in mould, and tablet machine is used to be pressed into pressed compact；(2) pressed compact is incubated a period of time under different pressure and temperature conditions, cools down release subsequently, it is thus achieved that block ternary boron-carbon-nitrogen material.Compared with prior art, present invention process is simple, cost is relatively low, and the component of the ternary boron-carbon-nitrogen material of synthesis can artificial adjustment.This material can have important realistic price and Research Significance as potential electronic component, transistor material in future.
Description
Technical field
The invention belongs to materialogy and physics's crossing domain, relate to a kind of multilamellar class heterojunction structure ternary boron
The synthetic method of carbon nitrogen functional material.
Background technology
Diamond is the material that known hardness is the highest, and its Vickers hardness is up to 98GPa, is traditional grinding, cutting tool
Ideal material.Its shortcoming is that oxidation resistance temperature is on the low side, easily aoxidizes after temperature is more than 800 DEG C.And c-BN is high temperature resistant, antioxygen
Change, but the hardness of business-like polycrystalline c-BN crystallite only has 33-45GPa, far below diamond, it is difficult to meet industrial applications
Requirement.1989, Liu foretold β-C3N4Crystal be a kind of potential superhard material (Liu, Cohen.Science, 1989,245,
841-842).But through the effort of people's more than ten years, β-C3N4The synthesis of crystal is still difficult to break through.Hereafter, start in the world
One design, upsurge of synthesizing new superhard material.Owing to C and BN is at the similarity of the aspect such as structure and phase transformation law, again
Because they some physical propertys exist great difference, it is intended that combine both obtain a kind of new have special
The material of the performances such as power, heat, electricity, light.The novel tertiary B-C-N material possessing bi-material advantage arises at the historic moment.Forefathers grind
Study carefully and be concentrated mainly on C and BN there is the BC of stoichiometric2N compound.In theory, by changing the content of C and BN, can set
Count out the B-C-N material of different component.Along with the progress of technology of preparing, Design Theory has the B-C-N material of superior physical properties
Material, will be expected to be synthesized in future.
Research shows, ternary B-C-N material is to exist with metastable state at normal temperatures and pressures.Due to its thermodynamic instability
Property, building-up process is prone to split-phase, brings the biggest difficulty to this material of synthesis.People use various synthetic method to obtain
Obtained B-C-N crystal or solid solution.Such as CVD (Kouvetakis, et al.Synth.Met., 1990,34,1-7), PVD
(Dinescu, et al.App1.Surf.Sci., 1998,129,692-696), chemical method (Riedel, et
Al.Adv.Mater., 1991,3,551-552；Hubacek, et al.J.Solid State Chem., 1995,114,258-
264), ballistic method (Yamada, et al.J.Am.Ceram.Soc., 1998,81,1941-1944), machine-alloying (Yao, et
Al.J.Appl.Phys., 1998,84,1412-1415), high temperature and high pressure method (Badzian.Mater.Res.Bull., 1981,
16,1385-1393；Solozhenko, et al Appl.Phys.Lett., 2001,78,1385-1387) etc..
According to synthetic method and the difference of technique, in the B-C-N material of forefathers' synthesis, the component of C and BN is within the specific limits
It is adjustable.Future can be by regulating the bonding mode of three kinds of atoms, and structure and performance to material carry out artificial regulation and control, come
Synthesis has the new function material of fanciful structures and superior physical properties.Graphite has similar crystal structure, phase with h-BN
Near atomic distance and thermal coefficient of expansion and different conduction types, meet the condition forming metal-insulator bulk heterojunction.
Ponomarenko etc. report to be clipped in h-BN Graphene as sandwich and form a kind of B-with peculiar transport property
C-N heterojunction structure (Ponomarenko, Geim, et al.Nature Physics, 2011,7,958-961).This heterogeneous
The B-C-N material of junction structure can become potential photoelectric device candidate material in future, have broad application prospects.At present,
Use the above-mentioned preparation technology cannot the B-C-N material of class heterojunction structure of synthesizing block.
Up to now, the most existing patent report relevant to the synthetic method of ternary B-C-N material.Japan Patent example
As: with BCl3It is that reactant uses chemical vapour deposition technique to prepare the BC of hexagonal phase with cyanogen methane2N thin film or powder body, then by BC2N
Powder and the one in Co, Fe, Ni and alloy thereof are blended in 1360 DEG C and carry out heat treatment acquisition Emission in Cubic boron carbon nitride (disclosure
Number JP01316460；JP94091954).Chinese patent is such as: the B-C-N presoma after ball milling is pressed by Tian Yongjun with catalytic powder
After certain mol proportion mixing, at 5.5GPa and 1400～1500 DEG C, process a period of time acquisition Emission in Cubic BC2N and B2CN crystal
(publication number CH1451472A)；Li Haipeng etc. use chemical vapour deposition technique to prepare the nanotube (publication number of boron carbon nitrogen
CN201210593109.1)。
Through the unremitting effort of people, the synthesis of B-C-N material there has been the biggest breakthrough.By graphite and h-BN are divided
The method that layer assembles, forms the interface of C and BN so that it is can be fully contacted, then use High Temperature High Pressure control between the layers
It is feasible that atomic bonding and dispersal direction and speed grow the B-C-N material of heterojunction structure.Use simple to operate, cost
Low high temperature and high pressure method synthesizes class heterojunction structure ternary boron carbon nitrogen functional material, and synthesis new function material is had weight
Want reference value.So far, there is not yet the Patents report of the B-C-N material of synthesis class heterojunction structure.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of method simple, effectively
The synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material.
The purpose of the present invention can be achieved through the following technical solutions: a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen
The synthetic method of functional material, it is characterised in that the method specifically includes following steps:
(1) by hexagonal boron nitride and graphite or graphene powder, under protective gas atmosphere, by certain mol proportion alternatively layered
Closed assembly is in mould, and uses tablet machine to be pressed into pressed compact；
(2) pressed compact is encapsulated on press, is incubated a period of time under different pressure and temperature conditions, release of lowering the temperature subsequently, obtains
Obtain block ternary boron carbon nitrogen sample.
High-purity hexagonal boron nitride described in step (1) and graphite or the purity of graphene powder > 99.0%, more preferably >
99.9%, most preferably > 99.99%, grain size is 1nm～10 μm, hexagonal boron nitride and the mol ratio of graphite (or Graphene)
It is 50: 1～1: 50.
High-purity hexagonal boron nitride described in step (1) and graphite or the purity of graphene powder > 99.9%, preferably >
99.99%.
The closed assembly number of plies of the hexagonal boron nitride described in step (1) and graphite or Graphene is at least two-layer.
Protection gas described in step (1) is vacuum or argon, and air pressure is less than 0.1GPa, and temperature range is 20～40 DEG C.
Mould described in step (1) is that arbitrary shape, size and material are made, and depends on press requirement, tablet machine pressure
Power is 5～30MPa.
Pressure described in step (2) is 1～100GPa, and temperature is 500～3000 DEG C, sample temperature retention time be 0.1～
24h。
Compared with prior art, it is an advantage of the current invention that operating procedure is simple, the impurity level that preparation process introduces is few, logical
Cross the mode of reactant alternatively layered closed assembly, it is possible to B-C-N material Atom combination and component to synthesis carry out essence
Really regulation and control, provide valuable Research foundation for follow-up experiment and application.
Accompanying drawing explanation
Fig. 1 is that layering assembles hexagonal boron nitride and graphite or the schematic diagram of graphene powder.
Detailed description of the invention
The present invention will the present invention is described in detail in conjunction with the drawings and specific embodiments below, and the present invention will provide following real
Execute example, it should be noted, however, that the enforcement of the present invention is not limited to implementation below.
Embodiment 1:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride 1 and graphite (or Graphene) powder 2, under argon atmosphere is protected, air pressure is less than
0.1GPa, temperature range is 20～40 DEG C, the mol ratio alternatively layered closed assembly by 1: 1 in mould, the number of plies be three layers (such as Fig. 1
Shown in), and use tablet machine to be pressed into pressed compact；Wherein, high-purity hexagonal boron nitride and the purity of graphite (or Graphene) powder >
99.0%, grain size is 1nm～10 μm；
Being encapsulated on press by pressed compact, be first forced into 5GPa, then heat, temperature is chosen as: 900～2100 DEG C of scopes
In select a temperature spot every 100 DEG C, be incubated 1h, release of lowering the temperature subsequently, it is thus achieved that block ternary boron carbon nitrogen sample.
Embodiment 2:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride and graphite (or Graphene) powder under argon atmosphere is protected, alternatively layered closed assembly is in mould
Having and being pressed into the method for pressed compact describes identical with embodiment 1, hexagonal boron nitride and the mol ratio 1 of graphite (or Graphene) powder
: 1, the number of plies is three layers；
Being encapsulated on press by pressed compact, be forced into 20GPa, remaining describes identical with embodiment 1.
Embodiment 3:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride and graphite (or Graphene) powder under argon atmosphere is protected, alternatively layered closed assembly is in mould
Having and being pressed into the method for pressed compact describes identical with embodiment 1, hexagonal boron nitride and the mol ratio 1 of graphite (or Graphene) powder
: 1, the number of plies is three layers；
Being encapsulated on press by pressed compact, be forced into 50GPa, remaining describes identical with embodiment 1.
Embodiment 4:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride and graphite (or Graphene) powder under argon atmosphere is protected, alternatively layered closed assembly is in mould
Having and being pressed into the method for pressed compact describes identical with embodiment 1, hexagonal boron nitride and the mol ratio 4 of graphite (or Graphene) powder
: 1, the number of plies is five layers；
Being encapsulated on press by pressed compact, be forced into 20GPa, remaining describes identical with embodiment 1.
Embodiment 5:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride and graphite (or Graphene) powder under argon atmosphere is protected, alternatively layered closed assembly is in mould
Having and being pressed into the method for pressed compact describes identical with embodiment 1, hexagonal boron nitride and the mol ratio 4 of graphite (or Graphene) powder
: 1, the number of plies is five layers；
Being encapsulated on press by pressed compact, be forced into 50GPa, remaining describes identical with embodiment 1.
Embodiment 6:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By high-purity hexagonal boron nitride and graphite (or Graphene) powder under argon atmosphere is protected, alternatively layered closed assembly is in mould
Having and being pressed into the method for pressed compact describes identical with embodiment 1, hexagonal boron nitride and the mol ratio 4 of graphite (or Graphene) powder
: 1, the number of plies is five layers:
Being encapsulated on press by pressed compact, be forced into 80GPa, remaining describes identical with embodiment 1.
Embodiment 7:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By purity > 99.99%, grain size is 1 μm～high-purity hexagonal boron nitride of 10 μm and graphite (or Graphene) powder
End, under argon atmosphere is protected, air pressure is less than 0.1 GPa, and temperature range is 20～40 DEG C, by the mol ratio alternatively layered of 50: 1
Closed assembly is in mould, and the number of plies is three layers, and uses tablet machine to be pressed into pressed compact, and mould is that arbitrary shape, size and material are made,
Depend on that press requirement, tablet machine pressure are 5MPa；
Being encapsulated on press by pressed compact, be first forced into 1GPa, then heat, temperature is chosen as: at 1000～3000 DEG C of models
Select a temperature spot every 100 DEG C in enclosing, be incubated 24h, release of lowering the temperature subsequently, it is thus achieved that block ternary boron carbon nitrogen sample.
Embodiment 8:
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, its synthetic method can be by following
Step is given:
By purity > 99.9%, grain size is high-purity hexagonal boron nitride and graphite (or Graphene) powder of 1nm～10nm
End, under argon atmosphere is protected, air pressure is less than 0.1GPa, and temperature range is 20～40 DEG C, by the mol ratio alternatively layered of 1: 50
Closed assembly is in mould, and the number of plies is three layers, and uses tablet machine to be pressed into pressed compact, and mould is that arbitrary shape, size and material are made,
Depend on that press requirement, tablet machine pressure are 30MPa；
Being encapsulated on press by pressed compact, be first forced into 100GPa, then heat, temperature is chosen as: at 500-2000 DEG C of model
Select a temperature spot every 100 DEG C in enclosing, be incubated 0.1h, release of lowering the temperature subsequently, it is thus achieved that block
Ternary boron carbon nitrogen sample.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as
Protection scope of the present invention.Such as, the present invention obviously can use the tablet machine of disposable type, and can produce the press of pressure
Equipment.Various heating method can be used to heat to sample.
It addition, the scope of each parameter that the present invention mentions includes the combination in any of any upper and lower bound, also include each
Any number scope that in specific embodiment, the occurrence of this parameter is constituted as the upper limit or lower values；All these scopes
All contain within the scope of the invention, simply for saving space, enumerate the most in the description.In this specification for table
Show numerical range symbol "～" represent the most any value including two end points.
It addition, each preferred aspect of the present invention is the most independent.Such as, the preferred scope of a parameter can be with it
The preferred scope of its parameter is combined, and all these technical schemes combined are within the scope of the present invention equally,
Simply for saving space, enumerate the most in the description.The technical scheme that can not combine because of these or numerical range
Outside clearly not mentioned by description and being regarded as beyond the scope of the invention.
Claims (4)
1. the synthetic method of a multilamellar class heterojunction structure ternary boron carbon nitrogen functional material, it is characterised in that the method is concrete
Comprise the following steps:
(1) by high-purity hexagonal boron nitride and graphite or graphene powder, under protective gas atmosphere, by certain mol proportion alternatively layered
Closed assembly is in mould, and uses tablet machine to be pressed into pressed compact；
(2) pressed compact is encapsulated on press, is incubated a period of time under different pressure and temperature conditions, cool down release subsequently, it is thus achieved that block
Body ternary boron carbon nitrogen sample；
High-purity hexagonal boron nitride described in step (1) and graphite or the purity of graphene powder > 99.0%, grain size is
The mol ratio of 1nm～10 μm, hexagonal boron nitride and graphite or Graphene is 50:1～1:50；
Protective gas atmosphere described in step (1) is vacuum or argon, and air pressure is less than 0.1GPa, and temperature range is 20～40 DEG C；
In step (1), the closed assembly number of plies of hexagonal boron nitride and graphite or Graphene is at least two-layer.
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material the most according to claim 1, its
Be characterised by, the high-purity hexagonal boron nitride described in step (1) and graphite or the purity of graphene powder 99.9%.
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material the most according to claim 1, its
Being characterised by, the tablet machine pressure described in step (1) is 5～30MPa.
The synthetic method of a kind of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material the most according to claim 1, its
Being characterised by, the pressure described in step (2) is 1～100GPa, and temperature is 500～3000 DEG C, sample temperature retention time be 0.1～
24h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410201072.2A CN103979975B (en) | 2014-05-13 | 2014-05-13 | A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410201072.2A CN103979975B (en) | 2014-05-13 | 2014-05-13 | A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103979975A CN103979975A (en) | 2014-08-13 |
| CN103979975B true CN103979975B (en) | 2016-08-24 |
Family
ID=51272180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410201072.2A Expired - Fee Related CN103979975B (en) | 2014-05-13 | 2014-05-13 | A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103979975B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944417A (en) * | 2015-06-01 | 2015-09-30 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene-boron nitride heterojunction |
| CN105481369B (en) * | 2015-12-10 | 2018-03-30 | 哈尔滨工业大学 | A kind of preparation method with the stratiform hexagonal boron nitride base composite ceramic for orienting thermal conduction characteristic |
| CN107117589B (en) * | 2017-05-25 | 2019-03-12 | 华侨大学 | A kind of high specific capacitance (BC) xNyOz material and its synthetic method |
| CN107215852A (en) * | 2017-06-22 | 2017-09-29 | 山东大学 | The method that a kind of utilization graphene and boron nitride nanosheet prepare boron carbon nitrogen nanometer sheet |
| CN109734465B (en) * | 2019-01-10 | 2021-08-06 | 南方科技大学 | Boron-skin-nitrogen-core nano polycrystalline material, preparation method thereof and superhard cutter |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759128B1 (en) * | 2002-07-05 | 2004-07-06 | The Regents Of The University Of California | Bulk superhard B-C-N nanocomposite compact and method for preparing thereof |
-
2014
- 2014-05-13 CN CN201410201072.2A patent/CN103979975B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759128B1 (en) * | 2002-07-05 | 2004-07-06 | The Regents Of The University Of California | Bulk superhard B-C-N nanocomposite compact and method for preparing thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electron Tunneling through Ultrathin Boron Nitride Crystalline Barriers;Liam Britnell et al;《NANO LETTERS》;20120301;第12卷;第1707-1710页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103979975A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103979975B (en) | A kind of synthetic method of multilamellar class heterojunction structure ternary boron carbon nitrogen functional material | |
| Peng et al. | Diffusion-controlled alloying of single-phase multi-principal transition metal carbides with high toughness and low thermal diffusivity | |
| Xiao et al. | Significant elastocaloric effect in a Fe-31.2 Pd (at.%) single crystal | |
| Ngo-Duc et al. | Vertical ZnO nanowire growth on metal substrates | |
| Zhou et al. | Significant enhancement in the thermoelectric performance of aluminum-doped ZnO tuned by pore structure | |
| CN103626172B (en) | A kind of preparation method of high conductive graphite paper | |
| JP2012106925A5 (en) | ||
| Guan et al. | Enhanced thermoelectric performance of quaternary Cu2–2 x Ag2 x Se1–x S x liquid-like chalcogenides | |
| Li et al. | Pressure and temperature-dependent Raman spectra of MoS2 film | |
| WO2005079353A3 (en) | Nanoscale metal paste for interconnect and method of use | |
| CN103498074A (en) | Novel Ni3Al-based self-lubricating composite material and preparing method thereof | |
| Bolokang et al. | Novel synthesis of metastable HCP nickel by water quenching | |
| CN103219089A (en) | Porous graphite or graphene/porous composite ceramic conductive material and preparation method thereof | |
| CN102002757B (en) | Method for controlling bismuth-sulfide polycrystalline thermoelectric material texture | |
| CN102694116A (en) | Method for preparing thermoelectric material with P-type nano-structure and bismuth telluride matrix | |
| CN106554006B (en) | A kind of carbon material, preparation method and applications | |
| CN103966533B (en) | A kind of diamond heat-conducting composite and preparation method thereof | |
| Han et al. | Thermoelectric properties of p-type semiconductors copper chromium disulfide CuCrS 2+ x | |
| CN104402450A (en) | Method for quickly preparing Ti2AlN ceramic powder on the basis of thermal explosion reaction at low temperature | |
| Chung et al. | Low-temperature formation of nanocrystalline SiC particles and composite from three-layer Si/C/Si film for the novel enhanced white photoluminescence | |
| WO2014154135A1 (en) | Aluminum oxide dispersion-strengthened titanium aluminum nitride ceramic composite and method for preparing same | |
| CN101311365B (en) | Method for preparing room-temperature ferromagnetic Fe doped ZnO nanometer wire | |
| CN106702347A (en) | Method for preparing rare-earth hexaboride nano material taking carbon cloth as base | |
| CN100546908C (en) | A kind of synthetic method of aluminum carbide nano belt | |
| Lee et al. | Ammonium fluoride-activated synthesis of cubic δ-TaN nanoparticles at low temperatures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20190513 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |