CN104746144A - Preparation method of tin disulfide single crystal nanosheet - Google Patents
Preparation method of tin disulfide single crystal nanosheet Download PDFInfo
- Publication number
- CN104746144A CN104746144A CN201510178074.9A CN201510178074A CN104746144A CN 104746144 A CN104746144 A CN 104746144A CN 201510178074 A CN201510178074 A CN 201510178074A CN 104746144 A CN104746144 A CN 104746144A
- Authority
- CN
- China
- Prior art keywords
- preparation
- single crystal
- tin disulfide
- heating zone
- horizontal pipe
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 title claims abstract description 18
- 239000002135 nanosheet Substances 0.000 title abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 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
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims description 27
- 229910052618 mica group Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002055 nanoplate Substances 0.000 claims description 14
- 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
- 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
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000001307 helium Substances 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
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000005303 weighing Methods 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910021389 graphene Inorganic materials 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition-metal sulphides Chemical class 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 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
- 230000007812 deficiency Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005669 field 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
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- TUTLDIXHQPSHHQ-UHFFFAOYSA-N tin(iv) sulfide Chemical compound [S-2].[S-2].[Sn+4] TUTLDIXHQPSHHQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 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
- 238000002474 experimental method Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 235000016768 molybdenum Nutrition 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 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
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- C30B29/10—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
Landscapes
- 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 specifically, a kind of preparation of single crystal nanoplate is related to.
Background technology
Two-dimensional layer material is the class type material risen in recent years, this kind of material is otherwise known as Van der Waals crystal, its notable feature combines with stronger covalent linkage or ionic linkage in its molecular layer, be then rely on more weak van der Waals interaction power to be bonded together between molecular layer, therefore these materials are easy to the nanometer sheet structure forming unimolecular layer or several molecular layer.Wherein, foremost two-dimensional layer material surely belongs to Graphene, it be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene in year in 2004 by the physicist An Deliegaimu of Univ Manchester UK and student's Constant Ting Nuowoxiaoluofu thereof) find, this discovery makes these two physicists obtain the physics Nobel prize of 2010.Because Graphene has excellent optics, electricity, mechanics and thermal property, therefore there is huge potential using value in fields such as electronic information, mechanics of communication, biology, catalysis, sensings.But, the band gap width (E of Graphene
g) be 0eV, this defect greatly limit the application of Graphene in semiconductor electronics and opto-electronics.
Recent research shows that magnesium-yttrium-transition metal disulphide (molybdenumdisulphide, tungsten disulfide, two selenizing molybdenums, two tungsten selenide etc.) is a kind of two-dimensional semiconductor material of excellence.Relative to Graphene, transition-metal sulphides has desirable bandgap structure, and this feature makes them have great application potential at microelectronics and optoelectronic areas, with traditional silicon, II-VI compares with III-V group semi-conductor material, transition-metal sulphides two-dimensional nanostructure thickness is adjustable, all can obtain easily from individual layer to multilayer, make its grid modulation being beneficial to device and the High Density Integration (R.Cheng at longitudinal direction, S.Jiang, Y.Chen, Y.Liu, N.Weiss, H.C.Cheng, H.Wu, Y.Huang and X.F.Duan.Few-layermolybdenum disulfide transistors and circuits for high-speed flexibleelectronics.Nature Communication, 2014, 5), these two-dimensional material surface unusual light, there is no the outstanding key of chemistry, this feature makes current carrier avoid the impact of trap states, thus can obtain higher carrier mobility (RadisavljevicB, RadenovicA, BrivioJ, GiacomettiVand KisA.Single-layer MoS
2transistors.Nature Nanotechnology, 2011,6,147-150), in addition, natural two-dirnentional structure makes itself and flexible substrates have good compatibility, be expected to become desirable flexible device material (O.Lopez-Sanchez, D.Lembke, M.Kayci, A.Radenovic and A.Kis.Ultrasensitive photodetectors based on monolayerMoS
2.Nature Nanotechnology, 2013,8,497-501).
Except transition-metal sulphides, other metal chalcogenide compound also has excellent physical and chemical performance.Be exactly comparatively typically wherein tin disulfide (SnS
2), tin disulfide has typical CI
2type laminate structure, band gap magnitude, between 2.2-2.35eV, is often used to the fields such as semiconductor electronics, photoelectrocatalysis, energy storage.Such as, the SnS of several molecular layers thick
2field-effect transistor is successfully prepared, and its ON/OFF current ratio is up to 10
6(D.De, J.Manongdo, S.See, V.Zhang, A.Guloy and H.Peng.High on/off ratio field effect transistors based on exfoliatedcrystalline SnS
2nano-membranes.Nanotechnology, 2013,24) deficiency of Graphene in semiconductor electronics and opto-electronics application, is therefore expected to make up; In addition, SnS
2also possess excellent catalytic activity, can be used as photoelectrochemical cell cathode material catalytic water and decompose, individual layer SnS
2photoelectrolysis water efficiency can reach the visible ray efficiency of conversion of 38.7%, is current maximum value (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-LayersRealizing Efficient Visible-Light WaterSplitting.AngewandteChemie-International Edition.2012,51,8727-8731); In addition, research prove by with the Material cladding such as Graphene, tin disulfide may be used in lithium ion battery, and cell integrated capacity can 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-SnS
2hybrids with superior rate capability for lithium ion storage.Energy & Environmental Science, 2012,5,5226-5230).
So far, two-dimentional SnS is prepared
2the method of single crystal nanoplate mainly comprises physics stripping method (D.De, J.Manongdo, S.See, V.Zhang, A.Guloy and H.Peng.High on/off ratiofield effect transistors based on exfoliated crystalline SnS
2nano-membranes.Nanotechnology, 2013,24), hydrothermal synthesis method (B.Luo, Y.Fang, B.Wang, J.S.Zhou, H.H.Song and L.J.Zhi.Two dimensionalgraphene-SnS
2hybrids with superior rate capability for lithium ionstorage.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 depositionof SnS
2nanowall arrays with improved electrochemical performance forlithium ion battery.Materials Letters.2010,64,2350-2353) etc.For semiconductor electronics application, these preparation methods have respective deficiency.Such as physics stripping method, although can obtain high-quality SnS
2nanometer sheet, but this method poor repeatability, the nanometer sheet area prepared is relatively little, quantity is few, is not suitable for extensive electron device integrated; The SnS that hydrothermal synthesis method obtains
2nanometer sheet pattern heterogeneity and crystallinity is poor, surface imperfection is more, can reduce carrier mobility.
Therefore, need to provide that a kind of area is large, grain-size large, good uniformity and the high SnS of quality
2the preparation method of nanometer sheet.
Summary of the invention
The technical problem that will solve of the present invention is to provide that a kind of area is large, grain-size is large, good uniformity and the high SnS of quality
2the preparation method of nanometer sheet.
For solving the problems of the technologies described above, the present invention adopts as following technical proposals:
A preparation method for tin disulfide single crystal nanoplate, it comprises the steps:
1) substrate is positioned over horizontal pipe furnace heating zone downstream area;
2) SnS is weighed
2powder, and be placed in high-temperature resistant container, then place it in described horizontal pipe furnace heating zone;
3) weigh sulphur powder, and be placed in another high-temperature resistant container, then place it in described horizontal pipe furnace heating zone upstream region;
4) described horizontal tube furnace pressure is reduced;
5) in described horizontal pipe furnace, be filled with rare gas element, make pressure in described stove be returned to normal pressure, keep the rare gas element of certain flow rate simultaneously;
6) described horizontal tube furnace temperature is risen to 650-750 DEG C;
7) by described horizontal pipe furnace heating zone Temperature fall to room temperature.
Aforesaid method is that normal atmosphere vapor deposition legal system is for big area, large size SnS
2nanometer sheet, is characterized in that with tin disulfide (SnS
2) and sulphur powder (S) be source material, with sheet mica (mica) for substrate, rare gas element is carrier gas, under hot conditions on sheet mica deposition obtain big area, large-sized SnS
2nanometer sheet.
Described high-temperature resistant container can be ceramic boat, corundum boat or quartz boat.
Described heating zone refers to the region residing for horizontal pipe furnace heating rod; Described heating zone upstream region and the corresponding flow rate of carrier gas direction of downstream area, refer to the top and bottom of horizontal pipe furnace heating zone, as shown in Figure 1.
Described substrate is high temperature resistant and level and smooth substrate, such as sheet mica, silicon-dioxide, quartz plate or sapphire sheet etc., and described substrate needs to cut into suitable specification.Described substrate is positioned over described heating zone downstream area (as shown in Figure 1), the position of distance heating region 5-20cm.Preferably, described substrate is sheet mica, and more preferably, described substrate is fluorophlogopite sheet.In one embodiment, sheet mica is cut into the specification of 2cm × 3.5cm.SnS
2nanometer sheet growth requires higher to the degree of cleaning of substrate material, and preferably, the upper layer be exposed to by sheet mica in air is removed.
Preferably, SnS
2powder is high purity SnS
2powder, purity is not less than 99%.
Described sulphur powder and SnS
2mol ratio be greater than 300.The high-temperature resistant container that sulphur powder is housed is positioned over the position of the heating zone upstream region 15-30cm of distance horizontal pipe furnace.
Preferably, vacuumize to reduce horizontal tube furnace pressure with mechanical pump, preferably, pressure drop, to below 0.1Pa, is filled with high purity rare gas element and makes pressure in stove be returned to atmospheric pressure.Described rare gas element is argon gas, nitrogen, helium or neon, is preferably argon gas.The flow velocity of described rare gas element remains between 20-200sccm.
Preferably, the temperature rise rate of described horizontal pipe furnace is between 10-25 DEG C/min, and the reacting by heating time is 5-30 minute.After heating terminates, treat that described horizontal pipe furnace heating zone Temperature fall is to room temperature, take out sheet mica substrate.
The SnS that the present invention prepares
2nanometer sheet has important researching value and application prospect widely in the fields such as solar cell, field-effect transistor, photocatalysis hydrogen production.
Beneficial effect of the present invention is as follows:
(1) preparation technology is simple, source material need be put into horizontal pipe furnace horizontal pipe furnace, carrier gas of having friendly relations by this experiment, mix up the program of heating just can, a step reacting by heating, therefore preparation process is quite simple;
(2) repeatability is high, namely prepares big area, large size SnS in this way
2the success ratio of nanometer sheet is high;
(3) controllability is strong, namely by changing the condition control SnS such as depositing time, vaporization temperature, source material quality
2the thickness, size, pattern etc. of nanometer sheet;
(4) synthesis cycle is short, and this method is reacted to from being heated to sampling of finally lowering the temperature, and only needs four or five hours, consuming time few;
(5) good crystallinity, because we adopt thermal evaporation, the SnS prepared under the high temperature conditions
2nanometer sheet, so the material obtained has higher degree of crystallinity.
(6) easily transfer to other substrate, be convenient to research and development and the application of extensive photoelectric device.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates SnS
2the growing apparatus schematic diagram of nanometer sheet.
Fig. 2 illustrates and grown SnS
2the sheet mica optical photograph of nanometer sheet.
Fig. 3 illustrates big area SnS
2the optical imagery of nanometer sheet.
Fig. 4 illustrates SnS
2nanometer sheet atomic force microscope (AFM) image and elevation information.
Fig. 5 illustrates SnS
2x ray diffracting data.
Fig. 6 illustrates SnS
2raman spectrum.
Fig. 7 illustrates the SnS of (a) hexagon shape
2nanometer sheet transmission electron microscope (TEM) bright field image; (b) SnS
2nanometer sheet low power high resolution transmission electron microscopy (HRTEM) photo, illustration is selected area electron diffraction (SAED), and a set of six sub symmetry diffraction spots prove that this nanometer sheet is monocrystalline; (c) high power HRTEM image; (d) energy dispersion X-ray spectrograph (EDX).
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
1. the preparation of sheet mica substrate:
1) specification that sheet mica becomes 2cm × 3.5cm is cut.
2) layer on sheet mica is removed with the tweezers that top is tapering, middle layer is for subsequent use as substrate.
2. prepare SnS
2nanometer sheet:
(1) described sheet mica substrate is put in horizontal pipe furnace heating zone downstream area, distance heating zone 5-20cm.
(2) SnS of 20mg is weighed
2powder (purity is not less than 99%) puts into ceramic boat, is then put in the heating zone of horizontal pipe furnace.
(3) the sulphur powder (excessive) weighing 1g is placed in another ceramic boat, is then put in the heating zone upstream region of horizontal pipe furnace, distance heated center 18cm.
(4) vacuumize with mechanical pump, by pressure drop in stove to below 0.1Pa.
(5) being filled with high purity argon makes pressure in horizontal pipe furnace get back to atmospheric pressure, and argon gas flow velocity remains on 80sccm.
(6) horizontal pipe furnace is heated to 700 DEG C, temperature rise rate remains on 20 DEG C/min, and heat-up time is 20 minutes.
(7) after heating terminates, treat that horizontal pipe furnace Temperature fall is to room temperature, take out sheet mica substrate.
As shown in Figure 2, mica substrate can be seen well-proportioned one deck yellow film.Utilize opticmicroscope to characterize, acquired results as shown in Figure 3.Mica substrate occurs hexagon or the rescinded angle hexagonal nanosheet of stochastic distribution, its diameter is between several micron to hundreds of micron.Atomic force microscope characterizes these nanometer sheet thickness of display and is about 100nm, and result as shown in Figure 4.X-ray diffraction characterizes these nanometer sheet and has 2T type hexagonal structure, and bottom it, crystal face is (0001) face, as shown in Figure 5.The Raman of nanometer sheet characterizes its Raman spectrum of display at 313.9cm
-1and 202.2cm
-1there are two peaks, respectively the A of corresponding tin sulfide
1gand E
graman peaks.Therefore Raman characterizes proves that these nanometer sheet are tin disulfide really, as shown in Figure 6.Transmission electron microscope characterization result is as shown in Figure 7: wherein Fig. 7 a is the TEM bright field image of a hexagon nanometer sheet; Fig. 7 b is the low power HRTEM picture of this nanometer sheet, be 0.32nm between the lattice fringe measured in figure, just with tin disulfide { 10-10} spacing is equal, the illustration SAED picture that region is corresponding for this reason, and a set of six sub symmetry diffraction spots prove that this nanometer sheet is monocrystalline; Fig. 7 c is the high power HRTEM image of corresponding 7b, and its lattice arrangement is consistent with the sulphur of tin disulfide or the arrangement of tin atom, is all Hexagonal array; Fig. 7 d is EDX data, has several element of sulphur, tin, copper, chromium, carbon in its display nanometer sheet, and Qi Zhongtong, chromium, carbon are from carbon supporting film and electronic microscope sample rod, and illustration shows that the atomic ratio of sulphur and tin is probably 2:1, proves that this nanometer sheet is tin disulfide.
Embodiment 2
1. the preparation of sheet mica substrate:
1) specification that sheet mica becomes 2cm × 3.5cm is cut.
2) layer on sheet mica is removed with the tweezers that top is tapering, middle layer is for subsequent use as substrate.
2. prepare SnS
2nanometer sheet:
(1) sheet mica substrate is put in horizontal pipe furnace heating zone downstream area, distance heating zone 5-20cm.
(2) SnS of 20mg is weighed
2powder (purity is not less than 99%) puts into ceramic boat, is then put in the heating zone heart of horizontal pipe furnace.
(3) the sulphur powder (excessive) weighing 0.5g is placed in another ceramic boat, is then put in the heated center upstream region of horizontal pipe furnace, distance heated center 15cm.
(4) vacuumize with mechanical pump, to make in stove pressure drop to below 0.1Pa.
(5) being filled with high-purity argon gas makes pressure in horizontal pipe furnace get back to atmospheric pressure, and argon gas flow velocity remains on 120sccm.
(6) described horizontal pipe furnace is heated to 650 DEG C, temperature rise rate remains on 20 DEG C/min, and heat-up time is 20 minutes.
(7) after heating terminates, treat that horizontal pipe furnace Temperature fall is to room temperature, take out sheet mica substrate.
Embodiment 3
1. the preparation of sheet mica substrate:
1) specification that sheet mica becomes 2cm × 3.5cm is cut.
2) layer on sheet mica is removed with the tweezers that top is tapering, middle layer is for subsequent use as substrate.
2. prepare SnS
2nanometer sheet:
(1) sheet mica substrate is put in horizontal pipe furnace heating zone downstream area, distance heated center 5-20cm.
(2) SnS of 30mg is weighed
2powder (purity is not less than 99%) puts into another ceramic boat, is then put in the heating zone of horizontal pipe furnace.
(3) the sulphur powder (excessive) weighing 1.6g is placed in another ceramic boat, is then put in the heating zone upstream region of horizontal pipe furnace, distance heating zone 22cm.
(4) vacuumize with mechanical pump, to make in stove pressure drop to below 0.1Pa.
(5) being filled with high pure nitrogen makes pressure in horizontal pipe furnace get back to atmospheric pressure, and nitrogen flow rate remains on 40sccm.
(6) described horizontal pipe furnace is heated to 750 DEG C, temperature rise rate remains on 20 DEG C/min, and heat-up time is 20 minutes.
(7) after heating terminates, treat that described horizontal pipe furnace Temperature fall is to room temperature, take out sheet mica substrate.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. a preparation method for tin disulfide single crystal nanoplate, is characterized in that, comprises the steps:
1) substrate is positioned over horizontal pipe furnace heating zone downstream area;
2) SnS is weighed
2powder, and be placed in high-temperature resistant container, then place it in described horizontal pipe furnace heating zone;
3) weigh sulphur powder, and be placed in another high-temperature resistant container, then place it in described horizontal pipe furnace heating zone upstream region;
4) described horizontal tube furnace pressure is reduced;
5) in described horizontal pipe furnace, be filled with rare gas element, make pressure in stove be returned to normal pressure, keep the rare gas element of certain flow rate simultaneously;
6) described horizontal tube furnace temperature is risen to 650-750 DEG C;
7) by described horizontal pipe furnace heating zone Temperature fall to room temperature.
2. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: described substrate is sheet mica, silicon-dioxide, quartz plate or sapphire sheet.
3. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: described substrate is positioned over the position of distance heating zone 5-20cm.
4. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: the container that sulphur powder is housed is positioned over the position of distance heated center 15-30cm.
5. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: described sulphur powder and SnS
2mol ratio be greater than 300.
6. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: SnS
2the purity more than 99% of powder.
7. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: described rare gas element is argon gas, nitrogen, helium or neon.
8. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: the Pressure Drop in described heating unit is low to moderate below 0.1Pa.
9. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: described horizontal pipe furnace temperature rise rate is 10-25 DEG C/min.
10. the preparation method of tin disulfide single crystal nanoplate according to claim 1, is characterized in that: step 6) described heat-up time is 5-30 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510178074.9A CN104746144B (en) | 2015-04-15 | 2015-04-15 | Preparation method of tin disulfide single crystal nanosheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510178074.9A CN104746144B (en) | 2015-04-15 | 2015-04-15 | Preparation method of tin disulfide single crystal nanosheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104746144A true CN104746144A (en) | 2015-07-01 |
| CN104746144B CN104746144B (en) | 2017-10-17 |
Family
ID=53586373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510178074.9A Active CN104746144B (en) | 2015-04-15 | 2015-04-15 | Preparation method of tin disulfide single crystal nanosheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104746144B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420815A (en) * | 2016-01-07 | 2016-03-23 | 中国科学院理化技术研究所 | Controllable preparation method of orthogonal-phase stannous sulfide two-dimensional single-crystal nanosheet |
| CN105463580A (en) * | 2016-01-07 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of cadmium selenide or cadmium sulfide two-dimensional single crystal nanosheet |
| 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 |
| CN109650354A (en) * | 2019-01-22 | 2019-04-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of preparation method of two dimension lead telluride nanometer sheet, using and a kind of nano material |
| CN109956495A (en) * | 2017-12-25 | 2019-07-02 | 中国科学院物理研究所 | Upright alternating expression petal-shaped stannic disulphide nano slice and preparation method thereof |
| CN110028098A (en) * | 2019-05-31 | 2019-07-19 | 南京倍格电子科技有限公司 | A kind of liquid phase stripping method preparation high concentration SnS2 nanometer sheet |
| CN113484302A (en) * | 2021-07-01 | 2021-10-08 | 中国科学院上海硅酸盐研究所 | SnS with capillary effect2Microsphere SERS substrate and preparation method and application thereof |
| CN114477270A (en) * | 2022-02-21 | 2022-05-13 | 福建师范大学 | Method for passivating and growing ultrathin stannous sulfide nanosheets by using sulfur |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614777A (en) * | 2013-10-15 | 2014-03-05 | 中国科学院理化技术研究所 | Preparation method of large-area single-layer and multi-layer molybdenum diselenide single crystal wafer |
| CN104178815A (en) * | 2014-08-18 | 2014-12-03 | 中国科学院理化技术研究所 | Method for epitaxially growing large-area single crystal ZnS film on single crystal ZnO substrate |
-
2015
- 2015-04-15 CN CN201510178074.9A patent/CN104746144B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614777A (en) * | 2013-10-15 | 2014-03-05 | 中国科学院理化技术研究所 | Preparation method of large-area single-layer and multi-layer molybdenum diselenide single crystal wafer |
| CN104178815A (en) * | 2014-08-18 | 2014-12-03 | 中国科学院理化技术研究所 | Method for epitaxially growing large-area single crystal ZnS film on single crystal ZnO substrate |
Non-Patent Citations (2)
| Title |
|---|
| GUOXIONG SU ET AL.: "Chemical Vapor Deposition of Thin Crystals of Layered Semiconductor SnS2 for Fast Photodetection Application", 《NANO LETTERS》 * |
| JING-KAI HUANG ET AL.: "Large-Area Synthesis of Highly Crystalline WSe2 Monolayers and Device Applications", 《ACSNANO》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105463580A (en) * | 2016-01-07 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of cadmium selenide or cadmium sulfide two-dimensional single crystal nanosheet |
| CN105463580B (en) * | 2016-01-07 | 2018-05-08 | 中国科学院理化技术研究所 | Preparation method of cadmium selenide or cadmium sulfide two-dimensional single crystal nanosheet |
| CN105420815A (en) * | 2016-01-07 | 2016-03-23 | 中国科学院理化技术研究所 | Controllable preparation method of orthogonal-phase stannous sulfide two-dimensional single-crystal nanosheet |
| CN109956495A (en) * | 2017-12-25 | 2019-07-02 | 中国科学院物理研究所 | Upright alternating expression petal-shaped stannic disulphide nano slice 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 |
| CN109650354A (en) * | 2019-01-22 | 2019-04-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of preparation method of two dimension lead telluride nanometer sheet, using and a kind of nano material |
| CN109650354B (en) * | 2019-01-22 | 2022-09-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method and application of two-dimensional lead telluride nanosheet and nanomaterial |
| CN110028098A (en) * | 2019-05-31 | 2019-07-19 | 南京倍格电子科技有限公司 | A kind of liquid phase stripping method preparation high concentration SnS2 nanometer sheet |
| 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 |
| CN113484302A (en) * | 2021-07-01 | 2021-10-08 | 中国科学院上海硅酸盐研究所 | SnS with capillary effect2Microsphere SERS substrate and preparation method and application thereof |
| CN114477270A (en) * | 2022-02-21 | 2022-05-13 | 福建师范大学 | Method for passivating and growing ultrathin stannous sulfide nanosheets by using sulfur |
| CN114477270B (en) * | 2022-02-21 | 2023-10-27 | 福建师范大学 | Method for growing ultrathin stannous sulfide nanosheets by sulfur passivation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104746144B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104746144B (en) | Preparation method of tin disulfide single crystal nanosheet | |
| Tao et al. | The effect of seed layer on morphology of ZnO nanorod arrays grown by hydrothermal method | |
| CN105420815B (en) | Controllable preparation method of orthogonal-phase stannous sulfide two-dimensional single-crystal nanosheet | |
| TWI608060B (en) | Large area deposition of graphene on substrates, and products including the same | |
| Kim et al. | Low-temperature wafer-scale growth of MoS2-graphene heterostructures | |
| Tang et al. | Confined van der Waals epitaxial growth of two-dimensional large single-crystal In2Se3 for flexible broadband photodetectors | |
| Wang et al. | Chemical vapor deposition growth of two-dimensional monolayer gallium sulfide crystals using hydrogen reduction of Ga2S3 | |
| CN102102220B (en) | Preparation method of graphene on diamond (111) surface | |
| Hu et al. | Controlled growth and photoconductive properties of hexagonal SnS 2 nanoflakes with mesa-shaped atomic steps | |
| CN104538288B (en) | A kind of device and method of direct growth atomic scale two-dimensional semiconductor hetero-junctions | |
| CN103643288A (en) | Preparation method of high-quality large-size monocrystal graphene | |
| Yang et al. | Shape evolution of two dimensional hexagonal boron nitride single domains on Cu/Ni alloy and its applications in ultraviolet detection | |
| CN103614777A (en) | Preparation method of large-area single-layer and multi-layer molybdenum diselenide single crystal wafer | |
| CN104389016A (en) | Method for quickly preparing large-size single-crystal graphene | |
| CN108069416B (en) | Ultra-clean graphene and preparation method thereof | |
| Wang et al. | Control growth of catalyst-free high-quality ZnO nanowire arrays on transparent quartz glass substrate by chemical vapor deposition | |
| CN103194795A (en) | Method for low-cost preparation of large-size monocrystal graphene | |
| CN108666358B (en) | Preparation method of transition metal chalcogenide and boron nitride or graphene heterojunction | |
| Chen et al. | Growth of 12-inch uniform monolayer graphene film on molten glass and its application in PbI 2-based photodetector | |
| CN107539976A (en) | A kind of method that carbon dioxide prepares ultra-clean graphene | |
| CN106315548B (en) | A kind of bis- selenizing molybdenum nanometer sheet core-shell structures of carbon fiber@and preparation method thereof | |
| Itoh et al. | Growth of spherical Si crystals on porous Si3N4 substrate that repels Si melt | |
| CN107119319B (en) | Cuprous iodide two-dimensional material, preparation and application thereof | |
| Luo et al. | Phase-controlled synthesis of SnS2 and SnS flakes and photodetection properties | |
| Liu et al. | A novel method for direct growth of a few-layer graphene on Al2O3 film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |