CN104746144B - Preparation method of tin disulfide single crystal nanosheet - Google Patents
Preparation method of tin disulfide single crystal nanosheet Download PDFInfo
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- CN104746144B CN104746144B CN201510178074.9A CN201510178074A CN104746144B CN 104746144 B CN104746144 B CN 104746144B CN 201510178074 A CN201510178074 A CN 201510178074A CN 104746144 B CN104746144 B CN 104746144B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000013078 crystal Substances 0.000 title claims abstract description 11
- 239000002135 nanosheet Substances 0.000 title abstract description 3
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims description 26
- 229910052618 mica group Inorganic materials 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002055 nanoplate Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 238000005303 weighing Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition-metal sulphides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016768 molybdenum Nutrition 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- KVXHGSVIPDOLBC-UHFFFAOYSA-N selanylidenetungsten Chemical class [Se].[W] KVXHGSVIPDOLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
-
- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a tin disulfide single crystal nanosheet, which comprises the following steps: 1) placing the substrate in a zone downstream of the heating zone of the horizontal tube furnace; 2) weighing SnS2 powder, placing the powder in a high-temperature resistant container, and then placing the container in a heating zone of a tube furnace; 3) weighing sulfur powder, placing the sulfur powder in another high-temperature-resistant container, and then placing the sulfur powder in an upstream area of a heating zone; 4) reducing the pressure in the horizontal tube furnace; 5) filling inert gas into the horizontal tube furnace to return the internal pressure of the horizontal tube furnace to normal pressure, and simultaneously keeping the inert gas at a certain flow rate; 6) raising the temperature of the horizontal tube furnace to 650-750 ℃; 7) and naturally cooling the heating area of the horizontal tube furnace to room temperature. The method has the advantages of simple preparation process, high repeatability, strong controllability, good crystallinity, easy transfer to other substrates and convenient research, development and application of large-scale photoelectric devices.
Description
Technical field
The present invention relates to nano material technical field of semiconductors.More particularly, to a kind of preparation of single crystal nanoplate.
Background technology
Two-dimensional layer material is the class new material risen in recent years, and this kind of material Van der Waals that are otherwise known as are brilliant
Body, it is noteworthy characterized by its molecular layer is combined with stronger covalent bond or ionic bond, and be then between molecular layer rely on compared with
Weak van der Waals interaction power is bonded together, therefore these materials are easily formed receiving for monolayer or several molecular layers
Rice chip architecture.Wherein, foremost two-dimensional layer material surely belongs to graphene, it be one kind by carbon atom with sp2Hybridized orbit group
It is in the flat film of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness into hexangle type.Graphene is in the quilt of year in 2004
Physicist An Deliegaimu and its student Constant the Ting Nuowoxiao love of Univ Manchester UK) find, this
It was found that making the physics Nobel Prize that this two physicists obtain 2010.Because graphene has excellent optics, electricity
Learn, mechanics and thermal property, therefore suffer from fields such as electronic information, mechanics of communication, biology, catalysis, sensings huge
Potential using value.However, band gap width (the E of grapheneg) it is 0eV, this defect greatly limit graphene in semiconductor
Application in electronics and opto-electronics.
Recent studies have indicated that magnesium-yttrium-transition metal disulphide (molybdenum disulfide, tungsten disulfide, two selenizing molybdenums, two tungsten selenides
Deng) it is a kind of excellent two-dimensional semiconductor material.Relative to graphene, transition-metal sulphides have preferable band gap knot
Structure, this feature makes them have great application potential in microelectronics and optoelectronic areas；With traditional silicon, II-VI and
III-V group semi-conductor material is compared, and transition-metal sulphides two-dimensional nanostructure thickness is adjustable, all can be light from individual layer to multilayer
Easily obtain, make its be beneficial to device grid modulation and longitudinal direction High Density Integration (R.Cheng, S.Jiang,
Y.Chen,Y.Liu,N.Weiss,H.C.Cheng,H.Wu,Y.Huang and X.F.Duan.Few-layer molybdenum
disulfide transistors and circuits for high-speed flexible electronics.Nature
Communication,2014,5)；These two-dimensional material surface unusual lights, no chemical dangling bond, this feature make carrier
From the influence of trap states, so as to obtain higher carrier mobility (RadisavljevicB, RadenovicA,
BrivioJ,GiacomettiV and KisA.Single-layer MoS2 transistors.Nature
Nanotechnology,2011,6,147-150)；In addition, natural two-dimensional structure makes it with flexible substrates with simultaneous well
Capacitive, is expected to turn into preferable flexible device material (O.Lopez-Sanchez, D.Lembke, M.Kayci, A.Radenovic
and A.Kis.Ultrasensitive photodetectors based on monolayer MoS2.Nature
Nanotechnology,2013,8,497-501)。
Except transition-metal sulphides, other metal chalcogenide compounds also have excellent physical and chemical performance.Wherein compared with
For it is typical be exactly stannic disulfide (SnS2), stannic disulfide has typical CI2Type layer structure, band gap magnitude is in 2.2-2.35eV
Between, it is commonly used for the fields such as semiconductor electronics, photoelectrocatalysis, energy storage.For example, the SnS of several molecular layers thicks2
Effect transistor is successfully prepared, its ON/OFF electric current ratio up to 106(D.De,J.Manongdo,S.See,V.Zhang,
A.Guloy and H.Peng.High on/off ratio field effect transistors based on
exfoliated crystalline SnS2Nano-membranes.Nanotechnology, 2013,24), therefore be expected to more
Mend the deficiency that graphene is applied in semiconductor electronics and opto-electronics；In addition, SnS2Excellent catalysis is also equipped with to live
Property, it can be used as the catalysis water decomposition of photoelectrochemical cell cathode material, individual layer SnS2Photoelectrolysis water efficiency can reach 38.7%
It can be seen that light conversion efficiency, be current maximum (Y.F.Sun, H.Cheng, S.Gao, Z.H.Sun, Q.H.Liu, Q.Liu,
F.C.Lei,T.Yao,J.F.He,S.Q.Wei and Y.Xie.Freestanding Tin Disulfide Single-
Layers Realizing Efficient Visible-Light Water Splitting.AngewandteChemie-
International Edition.2012,51,8727-8731)；In addition, research have shown that by with the Material cladding such as graphene,
Stannic disulfide can be used in lithium ion battery, and battery whole volume may be up to 650mA h g-1(B.Luo,Y.Fang,
B.Wang,J.S.Zhou,H.H.Song and L.J.Zhi.Two dimensional graphene-SnS2hybrids
with superior rate capability for lithium ion storage.Energy&Environmental
Science,2012,5,5226-5230)。
So far, two dimension SnS is prepared2The method of single crystal nanoplate mainly include physics stripping method (D.De,
J.Manongdo,S.See,V.Zhang,A.Guloy and H.Peng.High on/off ratio field effect
transistors based on exfoliated crystalline SnS2nano-
Membranes.Nanotechnology, 2013,24), hydrothermal synthesis method (B.Luo, Y.Fang, B.Wang, J.S.Zhou,
H.H.Song and L.J.Zhi.Two dimensional graphene-SnS2hybrids with superior rate
capability for lithium ion storage.Energy&Environmental Science,2012,5,5226-
5230), chemical bath deposition method (S.A.Liu, X.M.Yin, Q.Y.Hao, M.Zhang, L.M.Li, L.B.Chen, Q.H.Li,
Y.G.Wang and T.H.Wang.Chemical bath deposition of SnS2nanowall arrays with
improved electrochemical performance for lithium ion battery.Materials
Letters.2010,64,2350-2353) etc..For semiconductor electronics application, these preparation methods are suffered from each
Deficiency.Such as physics stripping method, although high-quality SnS can be obtained2Nanometer sheet, but the method poor repeatability, are prepared
Nanometer sheet area is relatively small, quantity is few, be not suitable for extensive electronic device integrated；The SnS that hydrothermal synthesis method is obtained2Nanometer
Piece pattern heterogeneity and crystallinity is poor, surface defect is more, can reduce carrier mobility.
Accordingly, it is desirable to provide the SnS that a kind of area is big, crystallite dimension is big, uniformity is good and quality is high2The preparation of nanometer sheet
Method.
The content of the invention
The technical problem to be solved of the present invention is to provide that a kind of area is big, crystallite dimension is big, uniformity good and quality height
SnS2The preparation method of nanometer sheet.
In order to solve the above technical problems, the present invention is using such as following technical proposals：
A kind of preparation method of stannic disulfide single crystal nanoplate, it comprises the following steps：
1) substrate is positioned over horizontal pipe furnace heating zone downstream area；
2) SnS is weighed2Powder, is placed in high-temperature resistant container, then places it in the horizontal pipe furnace heating zone；
3) sulphur powder is weighed, is placed in another high-temperature resistant container, then places it in the horizontal pipe furnace heating zone
Upstream region；
4) the horizontal tube furnace pressure is reduced；
5) inert gas is filled with into the horizontal pipe furnace, the stove internal pressure is returned to normal pressure, while keeping certain
The inert gas of flow velocity；
6) the horizontal tube furnace temperature is risen to 650-750 DEG C；
7) by horizontal pipe furnace heating zone Temperature fall to room temperature.
The above method is that normal atmosphere vapor deposition method prepares large area, large scale SnS2Nanometer sheet, it is characterized in that with curing
Tin (SnS2) and sulphur powder (S) be source material, with mica sheet (mica) for substrate, inert gas is in cloud under carrier gas, hot conditions
Deposition obtains large area, large-sized SnS on master slice2Nanometer sheet.
The high-temperature resistant container can be ceramic boat, corundum boat or quartz boat.
The heating zone refers to the region residing for horizontal pipe furnace heating rod；The heating zone upstream region and downstream area
Correspondence flow rate of carrier gas direction, refers to the top and bottom of horizontal pipe furnace heating zone, as shown in Figure 1.
The substrate is high temperature resistant and smooth substrate, such as mica sheet, silica, quartz plate or sapphire sheet
Deng the substrate needs to cut into suitable specification.The substrate is positioned over the heating zone downstream area (as shown in Figure 1),
Apart from heating region 5-20cm position.Preferably, the substrate is mica sheet, it is highly preferred that the substrate is fluorophologopite
Piece.In one embodiment, mica sheet is cut into 2cm × 3.5cm specification.SnS2Nanometer sheet is grown to the clear of backing material
Cleanliness requires higher, it is preferable that the upper layer being exposed to mica sheet in air is removed.
Preferably, SnS2Powder is high-purity SnS2Powder, purity is not less than 99%.
The sulphur powder and SnS2Mol ratio be more than 300.High-temperature resistant container equipped with sulphur powder is positioned over apart from horizontal tube
The heating zone upstream region 15-30cm of stove position.
Preferably, vacuumized to reduce horizontal tube furnace pressure with mechanical pump, it is preferable that pressure is down to below 0.1Pa,
Being filled with high-purity inert gas makes pressure in stove be returned to atmospheric pressure.The inert gas is argon gas, nitrogen, helium or neon
Gas, preferably argon gas.The flow velocity of the inert gas is maintained between 20-200sccm.
Preferably, between the heating rate of the horizontal pipe furnace is 10-25 DEG C/min, the heating response time is 5-30 points
Clock.After heating terminates, treat that horizontal pipe furnace heating zone Temperature fall, to room temperature, takes out mica sheet substrate.
The SnS that the present invention is prepared2Nanometer sheet is in the fields such as solar cell, field-effect transistor, photocatalysis hydrogen production
With important researching value and being widely applied prospect.
Beneficial effects of the present invention are as follows：
(1) preparation technology is simple, this experiment source material need to be put into horizontal pipe furnace horizontal pipe furnace, carrier gas of having friendly relations,
Mix up heating program just can, a step heating response, therefore preparation process is comparatively simple；
(2) repeatability is high, i.e., prepare large area, large scale SnS in this way2The success rate of nanometer sheet is high；
(3) controllability is strong, i.e., control SnS by changing the conditions such as sedimentation time, evaporating temperature, source material quality2Receive
Thickness, size, pattern of rice piece etc.；
(4) synthesis cycle is short, and this method is sampled from being heated to be reacted to finally cooling, it is only necessary to four or five hours, is taken few；
(5) good crystallinity, because we use thermal evaporation, the SnS prepared under the high temperature conditions2Nanometer sheet, so
The material arrived has higher crystallinity.
(6) other substrates are easily transferred to, are easy to the research and development and application of extensive photoelectric device.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows SnS2The grower schematic diagram of nanometer sheet.
Fig. 2 shows to grown SnS2The mica sheet optical photograph of nanometer sheet.
Fig. 3 shows large area SnS2The optical imagery of nanometer sheet.
Fig. 4 shows SnS2Nanometer sheet AFM (AFM) image and elevation information.
Fig. 5 shows SnS2X ray diffracting data.
Fig. 6 shows SnS2Raman spectrum.
Fig. 7 shows the SnS of (a) hexagon shape2Nanometer sheet transmission electron microscope (TEM) bright field image；(b)SnS2Nanometer sheet low power is high
Resolution Transmission Electron microscope (HRTEM) photo, illustration is SEAD (SAED), a set of six sub-symmetries diffraction spot card
This bright nanometer sheet is monocrystalline；(c) high power HRTEM images；(d) energy dispersion X-ray spectrometer (EDX).
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
1. the preparation of mica sheet substrate：
1) specification of the cutting mica sheet into 2cm × 3.5cm.
2) layer on mica sheet is removed with the tapering tweezers in top, it is standby using intermediate layer as substrate.
2. prepare SnS2Nanometer sheet：
(1) the mica sheet substrate is put in horizontal pipe furnace heating zone downstream area, apart from heating zone 5-20cm.
(2) 20mg SnS is weighed2Powder (purity is not less than 99%) is put into ceramic boat, is then put in horizontal tube
The heating zone of formula stove.
(3) sulphur powder (excess) for weighing 1g is placed in another ceramic boat, is then put in the heating zone of horizontal pipe furnace
Upstream region, apart from heated center 18cm.
(4) vacuumized with mechanical pump, pressure in stove is down to below 0.1Pa.
(5) being filled with high purity argon makes pressure in horizontal pipe furnace return to atmospheric pressure, and argon gas flow velocity is maintained at 80sccm.
(6) horizontal pipe furnace is heated to 700 DEG C, heating rate is maintained at 20 DEG C/min, the heat time is 20 points
Clock.
(7) after heating terminates, treat that horizontal pipe furnace Temperature fall, to room temperature, takes out mica sheet substrate.
As shown in Fig. 2 can see that well-proportioned one layer of yellow film in mica substrate.Table is carried out using light microscope
Levy, acquired results are as shown in Figure 3.Occur the hexagon of random distribution or rescinded angle hexagonal nanosheet in mica substrate, its is straight
Footpath is in several microns between hundreds of microns.AFM, which is characterized, shows that these nanometer sheet thickness are about 100nm, as a result as schemed
Shown in 4.X-ray diffraction, which characterizes these nanometer sheets, has 2T type hexagonal structures, and its bottom crystal face is (0001) face, as shown in Figure 5.
The Raman of nanometer sheet, which is characterized, shows its Raman spectrum in 313.9cm-1And 202.2cm-1There are two peaks, artificial gold is corresponded to respectively
A1gAnd EgRaman peaks.Therefore Raman, which is characterized, proves that these nanometer sheets are stannic disulfide really, as shown in Figure 6.Transmission electron microscopy
Mirror characterization result is as shown in Figure 7：Wherein Fig. 7 a are the TEM bright field images of a hexagon nanometer sheet；Fig. 7 b are this nanometer sheets
It is 0.32nm between the lattice fringe measured in low power HRTEM pictures, figure, just with { 10-10 } interplanar distance phase of stannic disulfide
It is the corresponding SAED pictures in this region Deng, illustration, a set of six sub-symmetries diffraction spot proves that this nanometer sheet is monocrystalline；Fig. 7 c are pair
7b high power HRTEM images are answered, its lattice arrangement is consistent with the arrangement of the sulphur or tin atom of stannic disulfide, all arranged in six sides
Row；Fig. 7 d are EDX data, and it, which shows, several elements of sulphur, tin, copper, chromium, carbon in nanometer sheet, and wherein copper, chromium, carbon comes from carbon branch
Film and electronic microscope sample rod are held, illustration shows that the atomic ratio of sulphur and tin is about 2:1, it was demonstrated that this nanometer sheet is stannic disulfide.
Embodiment 2
1. the preparation of mica sheet substrate：
1) specification of the cutting mica sheet into 2cm × 3.5cm.
2) layer on mica sheet is removed with the tapering tweezers in top, it is standby using intermediate layer as substrate.
2. prepare SnS2Nanometer sheet：
(1) mica sheet substrate is put in horizontal pipe furnace heating zone downstream area, apart from heating zone 5-20cm.
(2) 20mg SnS is weighed2Powder (purity is not less than 99%) is put into ceramic boat, is then put in horizontal tube
The heating zone heart of formula stove.
(3) sulphur powder (excess) for weighing 0.5g is placed in another ceramic boat, is then put in the heating of horizontal pipe furnace
Center upstream region, apart from heated center 15cm.
(4) vacuumized with mechanical pump, pressure in stove is down to below 0.1Pa.
(5) being filled with high-purity argon gas makes pressure in horizontal pipe furnace return to atmospheric pressure, and argon gas flow velocity is maintained at 120sccm.
(6) horizontal pipe furnace is heated to 650 DEG C, heating rate is maintained at 20 DEG C/min, the heat time is
20 minutes.
(7) after heating terminates, treat that horizontal pipe furnace Temperature fall, to room temperature, takes out mica sheet substrate.
Embodiment 3
1. the preparation of mica sheet substrate：
1) specification of the cutting mica sheet into 2cm × 3.5cm.
2) layer on mica sheet is removed with the tapering tweezers in top, it is standby using intermediate layer as substrate.
2. prepare SnS2Nanometer sheet：
(1) mica sheet substrate is put in horizontal pipe furnace heating zone downstream area, apart from heated center 5-20cm.
(2) 30mg SnS is weighed2Powder (purity is not less than 99%) is put into another ceramic boat, is then put in water
The heating zone of flat tube furnace.
(3) sulphur powder (excess) for weighing 1.6g is placed in another ceramic boat, is then put in the heating of horizontal pipe furnace
Area's upstream region, apart from heating zone 22cm.
(4) vacuumized with mechanical pump, pressure in stove is down to below 0.1Pa.
(5) being filled with high pure nitrogen makes pressure in horizontal pipe furnace return to atmospheric pressure, and nitrogen flow rate is maintained at 40sccm.
(6) horizontal pipe furnace is heated to 750 DEG C, heating rate is maintained at 20 DEG C/min, the heat time is
20 minutes.
(7) after heating terminates, treat that the horizontal pipe furnace Temperature fall, to room temperature, takes out mica sheet substrate.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (4)
1. a kind of preparation method of stannic disulfide single crystal nanoplate, it is characterised in that comprise the following steps：
1) substrate is positioned over horizontal pipe furnace heating zone downstream area；
2) SnS is weighed2Powder, is placed in high-temperature resistant container, then places it in the horizontal pipe furnace heating zone；
3) sulphur powder is weighed, is placed in another high-temperature resistant container, then places it in horizontal pipe furnace heating zone upstream
Region；
4) the horizontal tube furnace pressure is reduced；
5) inert gas is filled with into the horizontal pipe furnace, stove internal pressure is returned to normal pressure, while keeping the lazy of certain flow rate
Property gas；
6) the horizontal tube furnace temperature is risen to 650-750 DEG C；
7) by horizontal pipe furnace heating zone Temperature fall to room temperature；
The substrate is mica sheet, silica, quartz plate or sapphire sheet；
The substrate is positioned over apart from heating zone 5-20cm position；
Container equipped with sulphur powder is positioned over apart from heated center 15-30cm position；
Pressure in the heater is reduced to below 0.1Pa；
Step 6) horizontal pipe furnace heating rate be 10-25 DEG C/min, the heating response time be 5-30 minutes.
2. the preparation method of stannic disulfide single crystal nanoplate according to claim 1, it is characterised in that：The sulphur powder with
SnS2Mol ratio be more than 300.
3. the preparation method of stannic disulfide single crystal nanoplate according to claim 1, it is characterised in that：SnS2Powder it is pure
Degree more than 99%.
4. the preparation method of stannic disulfide single crystal nanoplate according to claim 1, it is characterised in that：The inert gas
For argon gas, nitrogen, helium or neon.
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| CN109956495B (en) * | 2017-12-25 | 2020-12-22 | 中国科学院物理研究所 | Vertical staggered petal-shaped tin disulfide nanosheet and preparation method thereof |
| CN108103580A (en) * | 2017-12-27 | 2018-06-01 | 广东工业大学 | A kind of preparation method of two sulphur stannic selenide single-crystal semiconductor material |
| CN108531981A (en) * | 2018-03-09 | 2018-09-14 | 广东工业大学 | A method of preparing two-dimentional indium trisulfide monocrystalline in mica substrate |
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| CN110028098B (en) * | 2019-05-31 | 2020-04-07 | 南京倍格电子科技有限公司 | High-concentration SnS prepared by liquid-phase stripping method2Nano-sheet |
| CN113484302B (en) * | 2021-07-01 | 2022-12-13 | 中国科学院上海硅酸盐研究所 | SnS with capillary effect 2 Microsphere SERS substrate and preparation method and application thereof |
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