CN106498492A - Method for preparing orthorhombic black phosphorus single crystal - Google Patents
Method for preparing orthorhombic black phosphorus single crystal Download PDFInfo
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- CN106498492A CN106498492A CN201610957176.5A CN201610957176A CN106498492A CN 106498492 A CN106498492 A CN 106498492A CN 201610957176 A CN201610957176 A CN 201610957176A CN 106498492 A CN106498492 A CN 106498492A
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- rhombic system
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000013078 crystal Substances 0.000 title claims abstract description 10
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims abstract description 28
- 229910052738 indium Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000010453 quartz Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003708 ampul Substances 0.000 claims description 19
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- JTDNNCYXCFHBGG-UHFFFAOYSA-L Tin(II) iodide Inorganic materials I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910001511 metal iodide Inorganic materials 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000003306 harvesting Methods 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- -1 graphite alkenes Chemical class 0.000 description 13
- 238000005538 encapsulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000012634 fragment Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WGVVTQUSFDMILB-UHFFFAOYSA-J triiodyloxystannyl iodate Chemical compound I(=O)(=O)[O-].[Sn+4].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] WGVVTQUSFDMILB-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method of an orthorhombic black phosphorus single crystal, which specifically comprises the following steps: the method comprises the steps of mixing a phosphorus raw material, metal indium and tin iodide, placing the mixture in a reactor, sealing the reactor, and preparing black phosphorus through optimized temperature programming and cooling, wherein the obtained black phosphorus has good crystallization property and high purity, the catalyst can be repeatedly used, the preparation process has low requirement on equipment, the preparation process is easy to realize, and great convenience is provided for the subsequent application and development of the black phosphorus.
Description
Technical field
The invention belongs to optoelectronic semiconductor two-dimensional material field, and in particular to one kind side of preparation of rhombic system black phosphorus material
Method.
Background technology
The development to material that develops rapidly of semiconductor electronic industry is put forward higher requirement.Graphene has started two dimension
The epoch of material, the carrier mobility (15000cm of its superelevation2/ V*s) and other superior physicochemical properties cause it
It is considered as the material for most possibly replacing silicon, but the characteristic that band gap is zero limits the development of Graphene.With graphite alkenes
Seemingly, black phosphorus is a kind of two-dimensional material of single element, there is Van der Waals force between layers, can obtain difference by way of peeling off
The flat crystal of the number of plies.Black phosphorus not only has the superhigh current carrying transport factor (200～50000cm of class Graphene2/ V*s), and
Its band gap can adjust (0.3eV～2.0eV) by the number of plies, compensate for the deficiency of Graphene.In addition, black phosphorus material internal
Electronics and photon show the anisotropy of height in lamella, are therefore suitable for the development of future electronic industry.
The research of black phosphorus at present is in the starting stage, and develops relatively slowly, is primarily due to currently without a kind of simple height
The synthetic method of effect.1914, Bridgman heated white phosphorus to 200 DEG C under the pressure of 1.2GPa, finds black phosphorus for the first time
Exist；Nineteen fifty-five, Germanization scholar Krebs, H. at ambient pressure, with mercury as catalyst, and using a small amount of black phosphorus as crystal seed,
At a temperature of 370 DEG C, white phosphorus is changed into black phosphorus；1981, the simple substance of Tokyo University scientist Maruyama, Y. using melting
Bismuth dissolves white phosphorus, and then Slow cooling recrystallization synthesizes the black phosphorus of needle-like.However, the severe toxicity and ignition quality of white phosphorus are limited
The application of these methods.2007, Nilges, Tom utilized Au, Sn and SnI4As combination catalyst, under vacuum conditions, plus
Hot red phosphorus obtains black phosphorus, but the introducing of noble metal improves production cost and the purity of black phosphorus decreases to 600 DEG C；
CA105133009A, CA105460910 and CA105565289 also disclose the improvement to the method, but former to temperature control and red phosphorus
The requirement of material is higher, and there is catalyst choice certain limitation (to be only limitted to Au, Sn, l2Or its product that reacts to each other) and simultaneously
Do not reuse；2010, Cheol-Min Park utilized high energy ball mill, synthesized the composite of red phosphorus and black phosphorus, but
High-energy ball milling method is difficult the pressure and temperature for accurately controlling inside reactor, affects the controllability of preparation process.Therefore current
The more commonly used synthetic method is high pressure (10kbar) method, but these methods have high requirement to laboratory apparatus.
Content of the invention
It is an object of the invention to provide a kind of with low cost, convenient and safe rhombic system black phosphorus method for preparing single crystal.
To achieve these goals, the present invention provides a kind of preparation method of rhombic system black phosphorus monocrystalline, wherein the method
Including：Phosphorus raw material, indium metal, stannic iodide are mixed, be placed in reactor, is tamping after excluding oxygen and by temperature programming and drop
Temperature prepares black phosphorus.
The present invention compared with prior art, employs reusable new catalyst, optimizes reaction temperature, simplifies
Heating process, shortens the reaction time.Other features and advantages of the present invention will give in subsequent specific embodiment part in detail
Describe in detail bright.
Description of the drawings
Accompanying drawing is invention to be further understood for providing, and constitutes a part for specification, concrete with following
Embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is intensification temperature lowering curve in black phosphorus preparation process；
Fig. 2 is the digital photograph of black phosphorus crystal in embodiment 3；
Fig. 3 is the X-ray diffractogram that tests after black phosphorus crystal grinding in embodiment 3
Fig. 4 is the X-ray diffractogram in embodiment 3 after black phosphorus crystal stripping；
Fig. 5 is the Raman spectrogram of black phosphorus crystal in embodiment 3；
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of preparation method of black phosphorus monocrystalline, and wherein the method includes：By phosphorus raw material, indium metal, iodate
Tin mixes, and is placed in reactor, will exclude oxygen rear enclosed, and prepare black phosphorus by temperature programming and temperature-fall period in reactor.
It is SnI wherein in stannic iodide4、SnI2Or both mixtures；Excluding oxygen can be by vacuumizing or being discharged with inert gas
The mode of air is realized；In Temperature Programmed Processes, first from room temperature elapsed time t1It is warming up to sublimation temperature T1, then through time t2
It is down to crystallization initiation temperature T2, elapsed time t3Reach crystallization final temperature T3.Wherein time t1、t2Do not limit, T1More than etc.
In 450 DEG C, preferably T1It is more than or equal to 535 DEG C；Time t3Relatively long, more than 4 hours, T3It is more than or equal to 416 DEG C, it is preferable that
T3It is more than or equal to 450 DEG C；T3The process of room temperature not limiting mode is down to, Temperature fall, air cooling-down, condensed water can be adopted
The modes such as cooling are realized.
According to the present invention, the phosphorus raw material can be understood as the presoma for preparing the black phosphorus monocrystalline, can be red phosphorus list
Matter, in order to improve the yield of rhombic system black phosphorus monocrystalline, under preferable case, the phosphorus element content of the red phosphorus simple substance is
More than 98%, more than more preferably 99.999% content, to the shape of the red phosphorus, there is no particular limitation, can adopt powder
Shape, sheet, block red phosphorus.Preferably, phosphorus raw material is red phosphorus, black phosphorus mixture, wherein the mass ratio of black phosphorus unlimited
Fixed.
According to the present invention, the indium metal coordinates stannic iodide to cause red phosphorus to be converted into black phosphorus, in order to improve orthorhombic
It is the yield of black phosphorus monocrystalline, under preferable case, the phosphide element content of the indium simple substance is more than 98%, more preferably 99.999%
More than content.
According to the present invention, the stannic iodide complexed metal indium causes red phosphorus to be converted into black phosphorus, wherein SnI4Preparation method is：
Tin simple substance and elemental iodine are mixed with mass ratio 1: 4, are dispersed in the solvent of glacial acetic acid and acetic anhydride (mass ratio 1: 1), are heated back
Stream, naturally cools to room temperature and separates out SnI4, recrystallized with organic solvent；SnI2Preparation method is：Excessive Sn and SnI4Mixed
Close, its mass ratio prepares SnI more than 2 by vapour deposition process2.
According to the present invention, the consumption of the phosphorus raw material, indium metal and stannic iodide can be changed in relative broad range, preferably feelings
Under condition, the weight ratio of the phosphorus raw material, indium metal and stannic iodide is 30-200: 2-10: 1, is still more preferably 50-100: 2-
5∶1.
Embodiment 1
By 0.3g red phosphorus, 0.02g indium metals, 0.01gSnI4Add in hyaline-quartz pipe, then quartz ampoule is carried out taking out very
Sky, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room temperature -60min-
535 DEG C -30min-450 DEG C -480min-416 DEG C-room temperature, temperature-fall period is by the way of Temperature fall.
The black phosphorus conversion ratio for obtaining is 52%, is block, and its size is about 0.5cm × 0.4cm.
Embodiment 2
By 0.3g red phosphorus, 0.1g indium metals, 0.01gSnI2Add in hyaline-quartz pipe, then quartz ampoule is carried out taking out very
Sky, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room temperature -60min-
535 DEG C -30min-450 DEG C -480min-416 DEG C-room temperature.
The black phosphorus conversion ratio for obtaining is 60%, is block, and its size is about 0.6cm × 05cm.
Embodiment 3
By 1g red phosphorus, 0.05g indium metals, 0.01gSnI4Add in hyaline-quartz pipe, then quartz ampoule is carried out taking out very
Sky, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room temperature -60min-
650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature, temperature-fall period is by the way of Temperature fall.
The black phosphorus conversion ratio for obtaining is 92%, is multiple bulks, and its size is about 1cm × 0.8cm.
Embodiment 4
By 1g red phosphorus, 0.05g indium metals, 0.01gSnI4Add high pressure in reactor, lead to argon gas 10min (flow velocitys～0.5mL/
S) air is discharged, is reacted according to following heating schedule after being tamping：- 60min-650 DEG C of -120min-550 DEG C of -480min- of room temperature
500 DEG C-room temperature, temperature-fall period is by the way of air cooling-down.
The black phosphorus conversion ratio for obtaining is 95%, is circular block shape, and its diameter is about 1.5cm.
Embodiment 5
Product black phosphorus in embodiment 3 is taken out, remaining catalyst (0.02g) is transferred to another quartz ampoule (internal diameter
1cm, long 10cm), 0.5g red phosphorus is added, then quartz ampoule is vacuumized, when vacuum reaches 1Pa encapsulation quartz ampoules,
React according to following heating schedule：- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of room temperature, temperature-fall period
By the way of Temperature fall.
Obtain black phosphorus conversion ratio and be about 90%, be multiple bulks, its size is about 0.8cm × 0.6cm.
Embodiment 6
Product black phosphorus in embodiment 4 is taken out, remaining catalyst (0.05g) is retained in autoclave, then plus
Enter 1g red phosphorus, lead to argon gas 10min (flow velocity～0.5mL/s) and discharge air, react according to following heating schedule after being tamping：Room temperature-
60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature, temperature-fall period is by the way of air cooling-down.
Obtain black phosphorus conversion ratio and be about 92%, be circular block shape, its diameter is about 0.8cm.
Embodiment 7
By 0.5g red phosphorus, 0.05g indium metals, 0.01gSnI2Add in hyaline-quartz pipe, then quartz ampoule is carried out taking out very
Sky, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room temperature -60min-
650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature, temperature-fall period is by the way of condensed water cools.
The black phosphorus conversion ratio for obtaining is 88%, is multiple bulks, and its size is about 0.5cm × 0.5cm.
Embodiment 8
By 1g red phosphorus, 0.1g indium metals, 0.02gSnI2Add in autoclave, lead to argon gas 10min (flow velocity～
Air is discharged 0.5mL/s), is reacted according to following heating schedule after being tamping：- 60min-650 DEG C -120min-550 DEG C of room temperature -
480min-500 DEG C-room temperature, temperature-fall period is by the way of air cooling-down.
The black phosphorus conversion ratio for obtaining is 90%, is circular block shape, and its diameter is about 1.5cm.
Embodiment 9
Product black phosphorus in embodiment 7 is taken out, remaining catalyst (0.02g) is transferred to another quartz ampoule (internal diameter
1cm, long 10cm), 1g red phosphorus is added, then quartz ampoule is vacuumized, when vacuum reaches 1Pa encapsulation quartz ampoules, pressed
React according to following heating schedule：- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of room temperature, temperature-fall period are adopted
The mode cooled with condensed water.
Obtain black phosphorus conversion ratio and be about 82%, be multiple bulks, its size is about 0.9cm × 0.8cm.
Embodiment 10
Product black phosphorus in embodiment 8 is taken out, remaining catalyst (0.1g) and a small amount of red phosphorus is retained in reaction under high pressure
In kettle, 1g red phosphorus is added, lead to argon gas 10min (flow velocity～0.5mL/s) and discharge air, anti-according to following heating schedule after being tamping
Should：- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of room temperature, side of the temperature-fall period using air cooling-down
Formula.
Obtain black phosphorus conversion ratio and be about 89%, be circular block shape, its diameter is about 09cm.
Embodiment 11
By 2g red phosphorus, 0.1g indium metals, 0.01gSnI4Add in autoclave, lead to argon gas 10min (flow velocity～
Air is discharged 0.5mL/s), is reacted according to following heating schedule after being tamping：- 60min-450 DEG C -30min-450 DEG C of room temperature -
480min-416 DEG C-room temperature.
The black phosphorus conversion ratio for obtaining is 55%, is multiple lump zone fragments, and its size is about 1cm × 0.5cm.
Embodiment 12
By 2g red phosphorus, 0.1g indium metals, 0.01gSnI2Add in autoclave, lead to argon gas 10min (flow velocity～
Air is discharged 0.5mL/s), is reacted according to following heating schedule after being tamping：- 60min-450 DEG C -30min-450 DEG C of room temperature -
480min-416 DEG C-room temperature.
The black phosphorus conversion ratio for obtaining is 57%, is multiple lump zone fragments, and its size is about 1cm × 0.6cm.
Embodiment 13
By 2g red phosphorus, 0.1g indium metals, 0.05gSnI2, 0.05gSnI4, add in autoclave, lead to argon gas 10min
(flow velocity～0.5mL/s) discharges air, reacts according to following heating schedule after being tamping：- 60min-450 DEG C of -30min-450 of room temperature
DEG C -480min-416 DEG C-room temperature.
The black phosphorus conversion ratio for obtaining is 80%, is multiple lump zone fragments, and its size is about 1cm × 0.6cm.
Embodiment 14
By 2g red phosphorus, 0.1g indium metals, 0.01gSnI2, 0.09gSnI4, add in hyaline-quartz pipe, then to quartz ampoule
Vacuumized, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room
- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of temperature, the side that temperature-fall period is cooled using condensed water
Formula.
The black phosphorus conversion ratio for obtaining is 85%, is multiple bulks, and its size is about 1cm × 0.5cm.
Embodiment 15
By 2g red phosphorus, 0.1g indium metals, 0.09gSnI2, 0.01gSnI4, add in hyaline-quartz pipe, then to quartz ampoule
Vacuumized, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).React according to following heating schedule：Room
- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of temperature, the side that temperature-fall period is cooled using condensed water
Formula.
The black phosphorus conversion ratio for obtaining is 86%, is multiple bulks, and its size is about 1cm × 0.5cm.
Embodiment 16
By 2g red phosphorus, 0.01g black phosphorus, 0.1g indium metals, 0.09gSnI2, 0.01gSnI4, add in hyaline-quartz pipe, so
Afterwards quartz ampoule is vacuumized, when vacuum reaches 1Pa encapsulation quartz ampoule (internal diameter 1cm, long 10cm).According to following heating journey
Sequence is reacted：- 60min-650 DEG C -120min-550 DEG C -480min-500 DEG C-room temperature of room temperature, temperature-fall period is using condensation water cooling
The mode of cooling.
The black phosphorus conversion ratio for obtaining is 92%, is multiple bulks, and its size is about 1cm × 0.8cm.
Claims (10)
1. a kind of preparation method of rhombic system black phosphorus monocrystalline, it is characterised in that the method includes：Phosphorus raw material and catalyst are mixed
Close, be placed in reactor and exclude oxygen and be tamping, black phosphorus is prepared by temperature programming and temperature-fall period.In Temperature Programmed Processes,
First from room temperature to sublimation temperature (T1), then it is down to crystallization initiation temperature (T2), through crystallization time (t3) reach crystallization eventually
Only temperature (T2), it is cooled to room temperature and harvests black phosphorus crystal, it is characterised in that catalyst is indium metal and stannic iodide, wherein stannic iodide
For SnI4、SnI2Or both mixtures, sublimation temperature (T1) it is higher than 450 DEG C,；Crystallization time (t3) more than or equal to 4 hours, knot
Brilliant final temperature (T3) it is more than or equal to 416 DEG C.
2. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1, wherein sublimation temperature (T1) be preferably more than
535 DEG C, crystallize final temperature (T3) it is preferably greater than 450 DEG C.
3. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1 and 2, wherein reactor are quartz ampoule, lead to
Cross the mode for vacuumizing to exclude oxygen and be tamping.
4. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1 and 2, wherein reactor are reaction under high pressure
Kettle, is tamping after excluding oxygen by way of vacuumizing or inert gas discharges air.
5. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-4, wherein crystallizes and terminates
Temperature (T3) process of room temperature is down to preferably using Temperature fall, air cooling-down, water-cooled cooling mode are realized.
6. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-5, wherein, red phosphorus, gold
Category indium, stannic iodide mass ratio be 30-200: 2-10: 1, preferably 50-100: 2-5: 1, reuse when input red phosphorus with
Remainder catalyst reaction produces black phosphorus, and red phosphorus is 10-50: 1 with remainder catalyst mass ratio.
7. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-6, wherein, phosphorus raw material is
Red phosphorus simple substance, in order to improve the yield of rhombic system black phosphorus monocrystalline, under preferable case, the P elements of the red phosphorus simple substance contain
Measure as more than 98%, more than more preferably 99.999% content, to the shape of the red phosphorus, there is no particular limitation, can adopt
Powder, sheet, block red phosphorus.Preferably, phosphorus raw material is red phosphorus, black phosphorus mixture.
8. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-6, wherein, indium metal
Phosphide element content is more than 98%, more than more preferably 99.999% content.
9. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-6, wherein SnI4Preparation side
Method is：Tin simple substance and elemental iodine are mixed with mass ratio 1: 4, are dispersed in the mixed solvent of glacial acetic acid and acetic anhydride, are heated to reflux,
Naturally cool to room temperature and separate out SnI4, recrystallized with organic solvent.
10. the preparation method of the rhombic system black phosphorus monocrystalline according to any one in claim 1-6, wherein SnI2Prepare
Method is：Sn and SnI4Mixing, its mass ratio prepare SnI more than 2 by vapour deposition process2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059138A (en) * | 2017-12-11 | 2018-05-22 | 昆明理工大学 | A kind of preparation method of high-purity black phosphorus |
| CN108557788A (en) * | 2018-03-16 | 2018-09-21 | 中国科学院深圳先进技术研究院 | A kind of black phosphorus method for preparing single crystal of low energy consumption |
| CN109305661A (en) * | 2017-07-27 | 2019-02-05 | 南京工业大学 | Method for preparing orthorhombic black phosphorus single crystal |
| CN109628994A (en) * | 2019-01-12 | 2019-04-16 | 河南大学 | A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation |
| CN109913942A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A kind of method that vapor transportation method prepares black phosphorus and adulterates black phosphorus monocrystalline |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN104630879A (en) * | 2015-02-28 | 2015-05-20 | 安庆美晶新材料有限公司 | Method for preparing black phosphorus monocrystal from high-purity red phosphorus under atmospheric pressure |
| CN105133009A (en) * | 2015-09-23 | 2015-12-09 | 清华大学 | Preparation method for orthorhombic crystal system black phosphorus monocrystalline |
| EP2975652A1 (en) * | 2014-07-15 | 2016-01-20 | Fundació Institut de Ciències Fotòniques | Optoelectronic apparatus and fabrication method of the same |
| CN105428983A (en) * | 2016-01-06 | 2016-03-23 | 电子科技大学 | Passive mode-locked laser based on black phosphorus optical saturation absorber |
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN105565289A (en) * | 2016-01-29 | 2016-05-11 | 西北大学 | Black phosphorus and phosphinidene preparing methods |
| CN105603517A (en) * | 2016-01-11 | 2016-05-25 | 上海交通大学 | Method for growing monocrystal black phosphorus based on solid-source chemical vapor deposition method |
-
2016
- 2016-11-01 CN CN201610957176.5A patent/CN106498492A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2975652A1 (en) * | 2014-07-15 | 2016-01-20 | Fundació Institut de Ciències Fotòniques | Optoelectronic apparatus and fabrication method of the same |
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN104630879A (en) * | 2015-02-28 | 2015-05-20 | 安庆美晶新材料有限公司 | Method for preparing black phosphorus monocrystal from high-purity red phosphorus under atmospheric pressure |
| CN105133009A (en) * | 2015-09-23 | 2015-12-09 | 清华大学 | Preparation method for orthorhombic crystal system black phosphorus monocrystalline |
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN105428983A (en) * | 2016-01-06 | 2016-03-23 | 电子科技大学 | Passive mode-locked laser based on black phosphorus optical saturation absorber |
| CN105603517A (en) * | 2016-01-11 | 2016-05-25 | 上海交通大学 | Method for growing monocrystal black phosphorus based on solid-source chemical vapor deposition method |
| CN105565289A (en) * | 2016-01-29 | 2016-05-11 | 西北大学 | Black phosphorus and phosphinidene preparing methods |
Non-Patent Citations (1)
| Title |
|---|
| MING ZHAO，ET AL.: "Understanding the growth of black phosphorus crystals", 《 THE ROYAL SOCIETY OF CHEMISTRY 2016》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305661A (en) * | 2017-07-27 | 2019-02-05 | 南京工业大学 | Method for preparing orthorhombic black phosphorus single crystal |
| CN108059138A (en) * | 2017-12-11 | 2018-05-22 | 昆明理工大学 | A kind of preparation method of high-purity black phosphorus |
| CN108557788A (en) * | 2018-03-16 | 2018-09-21 | 中国科学院深圳先进技术研究院 | A kind of black phosphorus method for preparing single crystal of low energy consumption |
| CN109913942A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A kind of method that vapor transportation method prepares black phosphorus and adulterates black phosphorus monocrystalline |
| CN109628994A (en) * | 2019-01-12 | 2019-04-16 | 河南大学 | A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation |
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