CN105420815A - Controllable method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet - Google Patents
Controllable method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet Download PDFInfo
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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
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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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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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
- C30B29/60—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
Abstract
The invention discloses a controllable method for preparing an orthogonal-phase stannous sulfide (SnS) two-dimensional monocrystalline nanosheet. The method includes the steps that a substrate is arranged on the downstream of a heating center of a horizontal tubular furnace and is 8-20 cm away from the heating center, SnS powder is placed in a high-temperature-resistant container, and the container is placed in the heating center of the horizontal tubular furnace; the tubular furnace is vaccumized, when the pressure intensity in the furnace is reduced to 0.1 Pa, inactive gas is injected into the furnace so that the pressure intensity in the tubular furnace can be 20-300 Torr again, and the flow speed of the gas is kept between 20 sccm to 200 sccm; the temperature of the heating center of the horizontal tubular furnace is raised to 600-800 DEG C, reaction time is 5-30 min, the substrate is taken out after the temperature in a cavity of the tubular furnace is naturally lowered to room temperature, and the stannous sulfide two-dimensional monocrystalline nanosheet grows on the surface of the substrate. The method is easy to operate, low in cost and high in controllability. Obtained SnS has the advantages of being large in size, good in uniformity and high in crystallinity, and the method has important research value and wide application prospects in the fields of field effect transistors, photoelectric detectors, photocatalytic hydrogen generation, lithium ion batteries and the like.
Description
Technical field
The present invention relates to two-dimensional semiconductor technical field.More specifically, the method for the two-dimentional single crystal nanoplate of a kind of controlled synthesis orthorhombic phase stannous sulfide (SnS) is related to.
Background technology
Van der Waals crystal is the class type material risen recent years, and its notable feature is with stronger covalent bonds in molecular layer, is then rely on more weak van der Waals interaction riding chain to be connected together between molecular layer.This feature makes this kind of material easily form ultra-thin two-dimension structure, and its thickness even can reach the thickness of unimolecular layer or several molecular layer.Ultra-thin two-dirnentional structure and the smooth flat of atom level make it be more conducive to electrostatic relative to body material, are beneficial to the electron device that development raceway groove is shorter, grid is less, the low power dissipation electron circuit that final height of formation is integrated.In addition, research proves that ultra-thin two-dimension structure has excellent mechanical property, and therefore these two-dimensional material have huge application potential in ultra-thin, ultralight collapsible photoelectric device.Recently, the research of two-dimensional material expands to other two-dimensional material from the Graphene of traditional metal-like properties, such as two-dimensional semiconductor material molybdenumdisulphide, two selenizing molybdenums, tin disulfide, black phosphorus etc., and wherein group IV-VI metal one sulphur compound is especially noticeable.Relative to Graphene, these semiconductor materials have desirable bandgap structure, and this feature makes them have larger application prospect at microelectronics and optoelectronic areas.In addition, group IV-VI metal one sulphur compound is a kind of eco-friendly material, and elementary composition, with low cost by what the earth enriched, show huge application potential in fields such as thermoelectricity electronics, solar cell, photochemical catalysis, super capacitor, ionization celies.(deKergommeaux,A.；Lopez-Haro,M.；Pouget,S.；Zuo,J.-M.；Lebrun,C.；Chandezon,F.；Aldakov,D.；Reiss,P.Synthesis,InternalStructure,andFormationMechanismofMonodisperseTinSulfideNanoplatelets.J.Am.Chem.Soc.2015,137,9943-9952.)
Stannous sulfide (SnS) is comparatively typical group IV-VI metal one sulphur compound, belongs to rhombic system, shows as the rock salt crystalline structure of distortion.It is a kind of P-type semiconductor, has a direct band gap (1.3eV) and an indirect band gap (1.07eV).The high absorption coefficient higher in visible region due to it and hypotoxicity, SnS is usually used as the light absorbing material in photovoltaic solar cell, for alternative costliness and the larger copper-indium-galliun-selenium (CIGS) of toxicity and cadmium telluride (CdTe).(Steinmann, V.; Jaramillo, R.; Hartman, K.; Chakraborty, R.; Brandt, R.E.; Poindexter, J.R.; Lee, Y.S.; Sun, L.Z.; Polizzotti, A.; Park, H.H.; Gordon, R.G.; Buonassisi, T.3.88%EfficientTinSulfideSolarCellsusingCongruentTherma lEvaporation.Adv.Mater.2014,26,7488-7492.) nearest research shows that SnS two-dimensional nanostructure has huge application prospect in micro-nano electronics and photoelectronics.Such as, the photo-detector based on ultra-thin SnS nano belt is successfully prepared, and its photoresponse time and photoconductive gain can reach 1ms and 104, is expected to make up the deficiency of Graphene in Semiconductor Optic Electronics field.(Deng, Z.T.; Cao, D.; He, J.; Lin, S.; Lindsay, S.M.; Liu, Y.SolutionSynthesisofUltrathinSingle-CrystallineSnSNanor ibbonsforPhotodetectorsviaPhaseTransitionandSurfaceProce ssing.ACSNano.2012,6,6197-6207.) in addition, Tritsaris utilizes first principle calculation to have studied individual layer, which floor and body SnS, result shows that the photoelectric property of SnS has significant thickness dependence, and this is that the application of SnS in micro-nano device provides theoretical direction.(Tritsaris, G.A., Malone, B.D., Kaxiras, E.Optoelectronicpropertiesofsingle-layer, double-layer, andbulktinsulfide:Atheoreticalstudy.JAPPLPHYS.2013,113.) meriting attention especially is thermal conductivity (Guo, the R.Q. that nearest report points out SnS, Wang, X.J., Kuang, Y.D., Huang, B.L.First-principlesstudyofanisotropicthermoelectrictran sportpropertiesofIV-VIsemiconductorcompoundsSnSeandSnS.P hys.Rev.B.2015, 92.), piezoelectric effect (Fei, R.X., Li, W.B., Li, J., Yand, L.GiantPiezoelectricityinMonolayerGroupIVMonochalcogenid es:SnSe, SnS, GeSeandGeS.GiantPiezoelectricityinMonolayerGroupIVMonoch alcogenides:SnSe, SnS, and spin transport (Shi GeSeandGeS.arXiv:1508.06222v2orarXiv:1508.06222.2015.), G., Kioupakis, E.AnisotropicSpinTransportandStrongVisible-LightAbsorban ceinFew-LayerSnSeandGeSe.NanoLett.2015,15,6926-6931.) there is obvious anisotropy, for regulation and control electricity, calorifics, optics etc. introduce a new degree of freedom, be conducive to exploitation based on anisotropic new function device.
So far, the method preparing SnS mainly comprises stripping method, (Brent, J.R.; Lewis, D.J.; Lorenz, T.; Lewis, E.A.; Savjani, N.; Haigh, S.J.; Seifert, G.; Derby, B.; O'Brien, P.Tin (II) Sulfide (SnS) NanosheetsbyLiquid-PhaseExfoliationofHerzenbergite:IV-VI MainGroupTwo-DimensionalAtomicCrystals.J.Am.Chem.Soc.201 5,137,12689-12696.) chemical synthesis, (Deng, Z.T.; Cao, D.; He, J.; Lin, S.; Lindsay, S.M.; Liu, Y.SolutionSynthesisofUltrathinSingle-CrystallineSnSNanor ibbonsforPhotodetectorsviaPhaseTransitionandSurfaceProce ssing.ACSNano.2012,6,6197-6207.) technique for atomic layer deposition ((Sinsermsuksakul, P.; Heo, J.; Noh, W.; Hock, A.S.; Gordon, R.G.AtomicLayerDepositionofTinMonosulfideThinFilms.Advan cedEnergyMaterials.2011,1,1116-1125.) etc.For semiconductor industry, these preparation methods have certain limitation.Such as stripping method, although can obtain high-quality SnS single crystal nanoplate, 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 pattern heterogeneity of chemosynthesis and crystallinity is poor, surface imperfection is more, can reduce carrier mobility.
Therefore, the novel method that a kind of controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate is provided is needed.
Summary of the invention
One object of the present invention is the method providing a kind of controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate.
In the present invention, applicant have employed a kind of new method to prepare high-quality SnS two dimension monocrystal nano-material.The method is simple to operate, repeatability is high, controllability is strong, and the SnS nanometer sheet area prepared is large, good uniformity, quality are high, and easily transfers to other substrate, is convenient to research and development and the application of extensive photoelectric device.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
A method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate, described method comprises the steps:
1) choose there is the growth substrates of the smooth substrate of atomically flating as SnS;
2) substrate is placed in the heated center downstream of horizontal pipe furnace, distance heated center 8-20cm, puts into high-temperature resistant container by SnS powder, high-temperature resistant container is placed in the heated center of horizontal pipe furnace;
3) tube furnace is vacuumized, when pressure drop is to 0.1Pa in stove, is filled with inactive gas and makes pressure in tubular type furnace chamber get back to 20-300Torr, and keep inactive gas flow velocity between 20-200sccm;
4) horizontal pipe furnace heated center is warming up to 600-800 DEG C, temperature rise rate remains between 5-20 DEG C/min, and the reaction times is 5-30 minute;
5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out substrate, namely substrate surface grows stannous sulfide two dimension single crystal nanoplate.Fluorophlogopite sheet surface can be observed and have grayish thin film, the SnS two dimension single crystal nanoplate namely prepared
Preferably, step 1) in, described substrate is sheet mica or sapphire.These two kinds of substrates are all hexagonal structure, and the surface of its atomically flating does not have dangling bonds, and these two kinds of substrates can be high temperature resistant.Orthorhombic phase SnS has laminate structure, and its inter-layer bonding force is more weak Van der Waals for, and therefore exposure is also very smooth does not in other words have dangling bonds for its natural cleavage plane.Utilize sheet mica or sapphire to be conducive to orthorhombic phase SnS transverse dispersion in two dimensional surface as substrate, form two-dimentional single crystal nanoplate.Otherwise, select to have the substrate of dangling bonds, as the substrate of monocrystalline substrate or other structures, the dangling bonds on its surface can introduce diffusion barrier, SnS molecule can be suppressed planar to move and two-dimensional growth, can not get the well-grown SnS two dimension single crystal nanoplate prepared by the present invention.
Preferably, step 1) in, described substrate is fluorophlogopite sheet.In a specific embodiment, fluorophlogopite sheet is divided into the rectangle of size 2cm*4cm, and by fluorophlogopite sheet from centre naturally cleaved one-tenth two thin slice, get new face of dissociating as aufwuchsplate.Fluorophlogopite sheet can be high temperature resistant, can provide stable growing environment for SnS crystal growth.It has six side's laminate structures in addition, and its cleavage surface has the surface of atomically flating and do not have dangling bonds, is conducive to SnS transverse growth in two dimensional surface, forms two-dimentional single crystal nanoplate.For the present invention, the selection of good substrate is the basis of successfully preparing two-dimentional monocrystalline SnS nanometer sheet.
Preferably, step 2) in, described SnS powder is high-purity SnS powder, and purity is not less than 99%.High purity SnS powder source is conducive to the growth of high purity SnS two dimension single crystal nanoplate.Otherwise, use low-purity SnS powder, defect may be introduced in the SnS nanometer sheet of growth.In addition, Impurity deposition can form forming core point or potential barrier on substrate, is unfavorable for SnS plane internal diffusion growth on substrate.
Preferably, step 2) in, described high-temperature resistant container is ceramic boat, corundum boat or quartz boat.These three kinds of containers are all high temperature resistant, can not produce impurity, or affect the thermal evaporation of SnS powder in heat-processed.
Preferably, step 3) in, described inactive gas is argon gas, nitrogen, helium or neon.
The present invention prepare orthorhombic phase SnS two dimension single crystal nanoplate method simple to operate, synthesis cost lower, whole preparation process only needs SnS powder and a synthesis device (high temperature process furnances), utilizes a step pyroreaction to obtain.
The invention also discloses a kind of employing preparation method described above and prepare orthorhombic phase stannous sulfide two dimension single crystal nanoplate.
Further, the invention discloses a kind of orthorhombic phase SnS two dimension single crystal nanoplate as above and make the application in photoelectric device, solar cell, field-effect transistor, visible-light detector field.
In prior art, patent CN102912300A discloses the method that SnS nanometer sheet is prepared in the thermal evaporation of a kind of catalyst-free assisted vacuum, its preparation method adopted is vacuum thermal evaporation, source material is Sn and S of 1:1, substrate is ito glass, its shortcoming is that the molten boiling point of source material is different, evaporates this bi-material simultaneously and can generate other products, as SnS
2and Sn
2s
3, cause product impure, detail as per the accompanying drawing 1 in patent CN102912300A.In addition, the substrate of this method selection is ito glass, the temperature tolerance of this substrate is relatively low, and the ITO layer on surface is the film particles of random deposition, substrate planeness is lower, and orientation of particles is uneven, cause the direction of growth of the nanometer sheet obtained uncontrollable, detail as per the accompanying drawing 2 to 4 in patent CN102912300A.The present invention in contrast, selects high-purity SnS as source material, and high temperature evaporation can guarantee purity and the unicity of source material, and SnS disproportionation reaction can not occur under the high temperature conditions, and pure thermal evaporation SnS is conducive to preparing high-purity SnS single crystal nanoplate.Substrate chooses resistant to elevated temperatures hexagonal structure single crystalline substrate in addition, and surface, without dangling bonds, is conducive to the growth of SnS planar diffusion, forms two-dimentional single crystal nanoplate.
Compared with prior art, in the present invention, applicant adopts physical vaporous deposition to be prepared orthorhombic phase SnS two dimension single crystal nanoplate, it is characterized in that with high-purity SnS powder for source material, fluorophlogopite sheet is substrate, argon gas (Ar) is carrier gas, deposits the orthorhombic phase SnS two dimension single crystal nanoplate obtaining big area, large domain for 5-30 minute under 600-800 DEG C and 20-300Torr condition on sheet mica.The SnS two dimension single crystal nanoplate that the present invention prepares has important researching value and wide application prospect in the fields such as photo-detector, solar cell, field-effect transistor.
Beneficial effect of the present invention is as follows:
(1) preparation technology is simple, and source material only need be put into tube furnace by this experiment, passes into carrier gas, set the program of heating just can, a step pyroreaction can obtain the two-dimentional single crystal nanoplate of orthorhombic phase SnS;
(2) controllability is strong, can the size, thickness, homogeneity etc. of control SnS nanometer sheet effectively by changing the conditions such as temperature of reaction, pressure, depositing time;
(3) repeatability is high, and the success ratio of the SnS two dimension single crystal nanoplate namely prepared in this way is high, and therefore repeatability better;
(4) synthesis cycle is short, and this method, from being heated to sampling of finally lowering the temperature, only needs four or five hours, consuming time shorter;
(5) good crystallinity, owing to using high-temperature hot method of evaporation, the SnS two-dimensional nano sheet prepared with this understanding has higher degree of crystallinity and purity.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the synthesis schematic diagram of SnS of the present invention two dimension single crystal nanoplate.
Fig. 2 illustrates the optical imagery (a) of SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1, lateral dimension statistical graph (b) and atomic force microscope (AFM) image and elevation information (c); The SnS two dimension optical imagery (d) of single crystal nanoplate, lateral dimension statistical graph (e) and atomic force microscope (AFM) image prepared by the embodiment of the present invention 2 and elevation information (f); The SnS two dimension optical imagery (g) of single crystal nanoplate, lateral dimension statistical graph (h) and atomic force microscope (AFM) image prepared by the embodiment of the present invention 3 and elevation information (i).
Fig. 3 illustrates X-ray diffraction (XRD) the data spectrogram of SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1.
Fig. 4 illustrates the Raman spectrogram of SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1.
Fig. 5 illustrates transmission electron microscope (TEM) bright field image (a) of single SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1, corresponding selected area electron diffraction (SAED) image (b), high resolution TEM (HRTEM) image (c) and energy spectrum analysis (EDS) spectrogram (d).
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) preparation of fluorophlogopite sheet substrate:
1) scissors is utilized sheet mica to be cut into little rectangular that is of a size of 2cm*4cm.
2) with tapering tweezers by fluorophlogopite sheet from centre naturally cleaved one-tenth two pieces, utilize the one side of newly riving as growth substrates.
(2) fluorophlogopite sheet substrate is put in downstream, diamond heating center successively, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.1g and put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 80Torr, and keep argon gas flow velocity between 60sccm.
(4) diamond heating center is warming up to 600 DEG C, temperature rise rate remains 20 DEG C/min, and the reaction times is 10 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out sheet mica substrate, can observe mica sheet surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
Fig. 1 illustrates the synthesis schematic diagram of SnS of the present invention two dimension single crystal nanoplate.In figure, the implication of each digitized representation is: 1.-silica tube, 2.-high-temperature resistant container, 3.-SnS powder, 4.-fluorophlogopite sheet, 5.-SnS two dimension single crystal nanoplate.
The optical imagery of the SnS two dimension single crystal nanoplate that (a) is prepared for the present embodiment in Fig. 2, (b) is lateral dimension statistical graph, and (c) is atomic force microscope (AFM) image and elevation information.
Fig. 3 illustrates X-ray diffraction (XRD) the data spectrogram of SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1.Except the stronger diffraction peak of 6 from sheet mica, a diffraction peak is only only had in XRD figure spectrum, this diffraction peak is in 32 ° of places, corresponding to orthorhombic phase SnS (JCPDFNo:39-0354, Pbnm) (040) crystal face, this show SnS nanometer sheet tend to along [010] direction growth and with (010) crystal face for growth basal plane.
Fig. 4 illustrates the Raman spectrogram of SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1.Characteristic Raman peak A in figure
gand B
3gprove that the nanometer sheet obtained is SnS.
Fig. 5 illustrates transmission electron microscope (TEM) bright field image (a) of single SnS two dimension single crystal nanoplate prepared by the embodiment of the present invention 1, corresponding selected area electron diffraction (SAED) image (b), high resolution TEM (HRTEM) image (c) and energy spectrum analysis (EDS) spectrogram (d).Selected area electron diffraction (SAED) image has a set of two-dimentional rhombus diffraction spot, proves that this nanometer sheet is the monocrystalline of orthorhombic phase.In high resolution TEM (HRTEM) image (c), the spacing identified in figure is 0.29nm, is consistent with (101) crystal face of orthorhombic phase SnS.D () energy spectrum analysis (EDS) shows this nanometer sheet sulfur-bearing and tin element, wherein C and Cu two kinds of elements are from copper mesh, and illustration shows that the atomic ratio of sulphur and tin is 1:1, proves that this nanometer sheet is SnS further.
Embodiment 2
(1) preparation of fluorophlogopite sheet substrate:
1) scissors is utilized sheet mica to be cut into little rectangular that is of a size of 2cm*4cm.
2) with tapering tweezers by fluorophlogopite sheet from centre naturally cleaved one-tenth two pieces, utilize the one side of newly riving as growth substrates.
(2) fluorophlogopite sheet substrate is put in downstream, diamond heating center successively, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.1g and put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 80Torr, and keep argon gas flow velocity between 60sccm.
(4) diamond heating center is warming up to 700 DEG C, temperature rise rate remains 20 DEG C/min, and the reaction times is 10 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out sheet mica substrate, can observe mica sheet surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
The optical imagery of the SnS two dimension single crystal nanoplate that (d) is prepared for the present embodiment in Fig. 2, (e) is lateral dimension statistical graph, and (f) is atomic force microscope (AFM) image and elevation information.
Embodiment 3
(1) preparation of fluorophlogopite sheet substrate:
1) scissors is utilized sheet mica to be cut into little rectangular that is of a size of 2cm*4cm.
2) with tapering tweezers by fluorophlogopite sheet from centre naturally cleaved one-tenth two pieces, utilize the one side of newly riving as growth substrates.
(2) fluorophlogopite sheet substrate is put in downstream, diamond heating center successively, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.1g and put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 300Torr, and keep argon gas flow velocity between 80sccm.
(4) diamond heating center is warming up to 800 DEG C, temperature rise rate remains 20 DEG C/min, and the reaction times is 20 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out sheet mica substrate, can observe mica sheet surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
The optical imagery of the SnS two dimension single crystal nanoplate that (g) is prepared for the present embodiment in Fig. 2, (h) is lateral dimension statistical graph, and (i) is atomic force microscope (AFM) image and elevation information.Integrated embodiment 1-3, the optical imagery of the SnS two dimension single crystal nanoplate prepared under 600 shown in Fig. 2 DEG C and 80Torr, 700 DEG C and 80Torr, 800 DEG C and 300Torr condition, shows that the SnS nanometer sheet obtained all has two-dirnentional structure.The lateral dimension statistical graph of the SnS two dimension single crystal nanoplate prepared under corresponding 600 DEG C and 80Torr, 700 DEG C and 80Torr, 800 DEG C and 300Torr condition, shows that the size of SnS nanometer sheet becomes large along with the increase of temperature and pressure gradually.And 600 DEG C and 80Torr, 700 DEG C and 80Torr, atomic force microscope (AFM) image of SnS single crystal nanoplate prepared under 800 DEG C and 300Torr condition and elevation information, illustrate that the thickness of SnS nanometer sheet becomes large along with the increase of temperature and pressure gradually.
Embodiment 4
(1) utilize the Sapphire Substrate of acetone and deionized water ultrasonic cleaning 1cm*1cm, nitrogen dries up;
(2) Sapphire Substrate is put in successively downstream, diamond heating center, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.2g and put into quartz boat, then quartz boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 50Torr, and keep argon gas flow velocity between 180sccm.
(4) diamond heating center is warming up to 750 DEG C, temperature rise rate remains 20 DEG C/min, and the reaction times is 20 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out substrate, can observe substrate surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
Embodiment 5
(1) utilize the Sapphire Substrate of acetone and deionized water ultrasonic cleaning 1cm*1cm, nitrogen dries up:
(2) Sapphire Substrate is put in successively downstream, diamond heating center, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.15g and put into corundum boat, then corundum boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 30Torr, and keep argon gas flow velocity between 200sccm.
(4) diamond heating center is warming up to 650 DEG C, temperature rise rate remains 20 DEG C/min, and the reaction times is 15 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out substrate, can observe substrate surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
Embodiment 6
(1) utilize the Sapphire Substrate of acetone and deionized water ultrasonic cleaning 1cm*1cm, nitrogen dries up:
(2) Sapphire Substrate is put in successively downstream, diamond heating center, distance heating source center 8-20cm.Weigh the high-purity SnS powder (purity is not less than 99%) of 0.3g and put into corundum boat, then corundum boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to vacuumize, when pressure drop is to 0.1Pa in tubular type furnace chamber, is filled with high-purity argon gas and makes pressure in tubular type furnace chamber get back to 250Torr, and keep argon gas flow velocity between 20sccm.
(4) diamond heating center is warming up to 800 DEG C, temperature rise rate remains 10 DEG C/min, and the reaction times is 25 minutes.
(5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out substrate, can observe substrate surface has grayish thin film, the SnS two dimension single crystal nanoplate namely prepared.
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 (9)
1. a method for controlled synthesis orthorhombic phase stannous sulfide two dimension single crystal nanoplate, it is characterized in that, described method comprises the steps:
1) choose there is the growth substrates of the smooth substrate of atomically flating as SnS;
2) substrate is placed in the heated center downstream of horizontal pipe furnace, distance heated center 8-20cm, puts into high-temperature resistant container by SnS powder, high-temperature resistant container is placed in the heated center of horizontal pipe furnace;
3) tube furnace is vacuumized, when pressure drop is to 0.1Pa in stove, is filled with inactive gas and makes pressure in tubular type furnace chamber get back to certain vacuum environment, and keep inactive gas flow velocity between 20-200sccm;
4) horizontal pipe furnace heated center is warming up to 600-800 DEG C, temperature rise rate remains between 5-20 DEG C/min, and the reaction times is 5-30 minute;
5) after reaction terminates, after tube furnace cavity temperature Temperature fall to room temperature, take out substrate, namely substrate surface grows SnS two dimension single crystal nanoplate.
2. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 1, is characterized in that: step 1) in, described substrate is sheet mica or sapphire.
3. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 2, it is characterized in that: step 1) in, described substrate is fluorophlogopite sheet, and by fluorophlogopite sheet from centre naturally cleaved one-tenth two thin slice, choose new cleavage surface as aufwuchsplate.
4. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 1, is characterized in that: step 2) in, described SnS powder is high-purity SnS powder, and purity is not less than 99%.
5. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 1, is characterized in that: step 2) in, described high-temperature resistant container is ceramic boat, corundum boat or quartz boat.
6. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 1, is characterized in that: step 3) in, described certain vacuum environment refers to that in chamber, pressure is 20-300Torr.
7. the method for controlled synthesis orthorhombic phase SnS two dimension single crystal nanoplate according to claim 1, is characterized in that: step 3) in, described inactive gas is nitrogen, helium or neon.
8. one kind adopts described preparation method as arbitrary in claim 1-7 to prepare the two-dimentional single crystal nanoplate of orthorhombic phase stannous sulfide.
9. orthorhombic phase stannous sulfide two dimension single crystal nanoplate as claimed in claim 8 is making the application in photoelectric device, solar cell, field-effect transistor, visible-light detector field.
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