CN105420815B - A kind of method of controllable preparation orthorhombic phase stannous sulfide two dimension single crystal nanoplate - Google Patents
A kind of method of controllable preparation orthorhombic phase stannous sulfide two dimension single crystal nanoplate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
The method that the present invention discloses a kind of two-dimentional single crystal nanoplate of controllable preparation orthorhombic phase stannous sulfide (SnS).This method includes for substrate being placed in the heated center downstream of horizontal pipe furnace, and apart from the 20cm of heated center 8, SnS powder is put into high-temperature resistant container, container is placed in the heated center of horizontal pipe furnace；To tubular type stove evacuation, when pressure is down to 0.1Pa in stove, being filled with inactive gas makes tube furnace intracavitary pressure return to 20 300Torr, and keeps gas flow rate between 20 200sccm；Horizontal pipe furnace heated center is warming up to 600 800 DEG C, the reaction time is 5 30 minutes, after tubular type furnace chamber temperature Temperature fall to room temperature, takes out substrate, substrate surface is that growth has stannous sulfide two dimension single crystal nanoplate.The method is simple to operate, cost is relatively low, controllability is stronger, the SnS of acquisition has the advantages that size is big, uniformity is good, crystallinity is high, has important researching value in the field such as scene effect transistor, photodetector, photocatalysis hydrogen production, lithium ion battery and is widely applied prospect.
Description
Technical field
The present invention relates to two-dimensional semiconductor technical field.More particularly, to a kind of controllable preparation orthorhombic phase stannous sulfide
(SnS) method of two-dimentional single crystal nanoplate.
Background technology
Van der Waals crystal is a kind of new material risen recent years, and it is noteworthy characterized by molecular layer with stronger
Covalent bonding together, and be connected together by weaker van der Waals interaction riding chain between molecular layer.This feature makes
This kind of material easily forms ultra-thin two-dimension structure, and its thickness can even reach the thickness of monolayer or several molecular layers.
Ultra-thin two-dimensional structure and the smooth flat of atom level make it be more conducive to electrostatic regulation and control relative to body material, beneficial to development raceway groove more
Electronic device short, grid is smaller, ultimately form highly integrated low power dissipation electron circuit.In addition, research has shown that ultra-thin two-dimension
Structure possesses excellent mechanical property, thus these two-dimensional materials possess in ultra-thin, ultralight foldable photoelectric device it is huge
Application potential.Recently, the research of two-dimensional material expands to other two-dimensional materials from the graphene of traditional metal-like properties, such as
Two-dimensional semiconductor material molybdenum disulfide, two selenizing molybdenums, stannic disulfide, black phosphorus etc., the wherein sulphur compound of group IV-VI metal one are especially
It is noticeable.Relative to graphene, these semi-conducting materials have preferable bandgap structure, and this feature makes them in microelectronics
And optoelectronic areas has bigger application prospect.In addition, the sulphur compound of group IV-VI metal one is a kind of environment-friendly material
Material, and by the earth enrich element form, cost is cheap, thermoelectricity electronics, solar cell, photocatalysis, super capacitor,
The fields such as ion battery show huge application potential.(de Kergommeaux,A.；Lopez-Haro,M.；Pouget,
S.；Zuo,J.-M.；Lebrun,C.；Chandezon,F.；Aldakov,D.；Reiss,P.Synthesis,Internal
Structure,and Formation Mechanism of Monodisperse Tin Sulfide
Nanoplatelets.J.Am.Chem.Soc.2015,137,9943-9952.)
Stannous sulfide (SnS) is the more typical sulphur compound of group IV-VI metal one, belongs to rhombic system, shows as turning round
Bent rock salt crystal structure.It is a kind of P-type semiconductor, possesses a direct band gap (1.3eV) and an indirect band gap
(1.07eV).Because it is in visible region higher high absorption coefficient and hypotoxicity, SnS is used frequently as photovoltaic solar electricity
Light absorbing material in pond, for substituting expensive and larger toxicity CIGS (CIGS) 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%Efficient Tin Sulfide Solar Cells using Congruent Thermal
Evaporation.Adv.Mater.2014,26,7488-7492.) recent studies have shown that SnS two-dimensional nanostructures are in micro-nano
There is huge application prospect in electronics and photoelectronics.For example, the photo-detector based on ultra-thin SnS nanobelts by into
Prepared by work(, its photoresponse time and photoconductive gain are expected to make up graphene in Semiconductor Optic Electronics neck up to 1ms and 104
Deficiency in domain.(Deng,Z.T.；Cao,D.；He,J.；Lin,S.；Lindsay,S.M.；Liu,Y.Solution
Synthesis of Ultrathin Single-Crystalline SnSNanoribbons for Photodetectors
Via Phase Transition and Surface Processing.ACS Nano.2012,6,6197-6207.) in addition,
Tritsaris have studied individual layer, several layers of and body SnS using first principle calculation, the results showed that SnS photoelectric property has notable
Thickness dependence, this application for being SnS in micro-nano device provides theoretical direction.(Tritsaris,G.A.；Malone,
B.D.；Kaxiras,E.Optoelectronic properties of single-layer,double-layer,and
bulk tin sulfide:A theoretical study.J APPL PHYS.2013,113.) especially to be worth noting be nearest
Report point out SnS thermal conductivity (Guo, R.Q.；Wang,X.J.；Kuang,Y.D.；Huang,B.L.First-
principles study of anisotropic thermoelectric transport properties of IV-VI
Semiconductor compounds SnSe and SnS.Phys.Rev.B.2015,92.), piezo-electric effect (Fei, R.X.,
Li,W.B.,Li,J.,Yand,L.Giant Piezoelectricity in Monolayer Group IV
Monochalcogenides:SnSe,SnS,GeSe and GeS.Giant Piezoelectricity in Monolayer
Group IV Monochalcogenides:SnSe,SnS,GeSe and GeS.arXiv:1508.06222v2or arXiv:
1508.06222.2015.) and spin transport (Shi, G.；Kioupakis,E.Anisotropic Spin Transport and
Strong Visible-Light Absorbance in Few-Layer SnSe and GeSe.Nano Lett.2015,15,
6926-6931.) there is obvious anisotropy, introduce a new free degree for regulation and control electricity, calorifics, optics etc., favorably
Anisotropic new function device is based in exploitation.
So far, preparing SnS method mainly includes 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)Nanosheets by Liquid-Phase Exfoliation of Herzenbergite:IV-VI
Main Group Two-Dimensional Atomic Crystals.J.Am.Chem.Soc.2015,137,12689-
12696.) chemical synthesis, (Deng, Z.T.；Cao,D.；He,J.；Lin,S.；Lindsay,S.M.；Liu,Y.Solution
Synthesis of Ultrathin Single-Crystalline SnSNanoribbons for Photodetectors
Via Phase Transition and Surface Processing.ACS Nano.2012,6,6197-6207.) atomic layer
Deposition technique ((Sinsermsuksakul, P.；Heo,J.；Noh,W.；Hock,A.S.；Gordon,R.G.Atomic Layer
Deposition of Tin Monosulfide Thin Films.Advanced Energy Materials.2011,1,
1116-1125.) etc..For semiconductor industry, these preparation methods have certain limitation.Such as stripping method,
Although the SnS single crystal nanoplates of high quality can be obtained, the method poor repeatability, the nanometer sheet area prepared is relatively
It is small, quantity is few, be not suitable for extensive electronic device and integrate；The SnS patterns heterogeneity and crystallinity of chemical synthesis are poor, surface
Defect is more, can reduce carrier mobility.
A kind of accordingly, it is desirable to provide new method of controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates.
The content of the invention
It is an object of the present invention to provide a kind of method of controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates.
In the present invention, applicant employs a kind of new method to prepare the SnS two dimension monocrystal nano-materials of high quality.
This method is simple to operate, it is repeated it is high, controllability is strong, the SnS nanometer sheet areas prepared are big, uniformity is good, quality is high, and
Other substrates are easily transferred to, are easy to the research and development and application of extensive photoelectric device.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of method of controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates, methods described comprise the following steps：
1) choose with growth substrates of the smooth substrate of atomically flating as SnS；
2) substrate is placed in the heated center downstream of horizontal pipe furnace, apart from heated center 8-20cm, SnS powder be put into
In high-temperature resistant container, high-temperature resistant container is placed in the heated center of horizontal pipe furnace；
3) to tubular type stove evacuation, when pressure is down to 0.1Pa in stove, being filled with inactive gas makes tube furnace intracavitary pressure
20-300Torr is returned to, and keeps inactive gas flow velocity between 20-200sccm；
4) horizontal pipe furnace heated center is warming up to 600-800 DEG C, between heating rate remains 5-20 DEG C/min, reaction
Time is 5-30 minutes；
5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, substrate is taken out, substrate surface grows
There is stannous sulfide two dimension single crystal nanoplate.It is observed that there is grayish thin film on fluorophologopite piece surface, that is, prepare
SnS two dimension single crystal nanoplates
Preferably, in step 1), the substrate is mica sheet or sapphire.Both substrates are all hexagonal structure, and it is former
Sub- level even curface does not have dangling bonds, and both substrates can high temperature resistant.Orthorhombic phase SnS has layer structure, its layer
Between adhesion be weaker Van der Waals for, therefore exposure is also very smooth in other words does not hang for its natural cleavage plane
Key.Be advantageous to orthorhombic phase SnS horizontal proliferation in two dimensional surface as substrate by the use of mica sheet or sapphire, it is single to form two dimension
Brilliant nanometer sheet.Conversely, substrate of the selection with dangling bonds, such as the substrate of monocrystalline substrate or other structures, its surface hangs
Diffusion barrier can be introduced by hanging key, can be suppressed SnS molecules and planar be migrated and two-dimensional growth, life that cannot be prepared by the present invention
Long good SnS two dimension single crystal nanoplates.
Preferably, in step 1), the substrate is fluorophologopite piece.In a specific embodiment, by fluorophologopite
Piece is divided into size 2cm*4cm rectangle, and fluorophologopite piece is naturally cleaved into two thin slices from centre, takes new dissociation face to make
For aufwuchsplate.Fluorophologopite piece energy high temperature resistant, stable growing environment can be provided for SnS crystal growths.It has six sides in addition
Layer structure, its cleavage surface have the surface of atomically flating and no dangling bonds, are advantageous to SnS and are laterally given birth in two dimensional surface
It is long, form two-dimentional single crystal nanoplate.For the present invention, the selection of good substrate is successfully to prepare two-dimentional monocrystalline SnS to receive
The basis of rice piece.
Preferably, in step 2), the SnS powder is high-purity SnS powder, and purity is not less than 99%.High-purity SnS powder
Source is advantageous to the growth of high-purity SnS two dimension single crystal nanoplates.Conversely, using low-purity SnS powder, may be in growth
Defect is introduced in SnS nanometer sheets.In addition, impurity, which is deposited on substrate, can form forming core point or potential barrier, it is unfavorable for SnS in substrate
Diffusion growth in upper plane.
Preferably, in step 2), the high-temperature resistant container is ceramic boat, corundum boat or quartz boat.These three containers are all resistance to
High temperature, impurity will not be produced in heating process, or influence the thermal evaporation of SnS powder.
Preferably, in step 3), the inactive gas is argon gas, nitrogen, helium or neon.
Method that the present invention prepares orthorhombic phase SnS two dimension single crystal nanoplates is simple to operate, synthesis cost is relatively low, whole to prepare
Process only needs SnS powder and a synthesis device (high temperature process furnances), can be obtained using a step pyroreaction.
Orthorhombic phase stannous sulfide two dimension monocrystalline is prepared using preparation method as described above the invention also discloses one kind
Nanometer sheet.
Further, the invention discloses a kind of orthorhombic phase SnS two dimensions single crystal nanoplate as described above to make photoelectricity
Application in device, solar cell, field-effect transistor, visible-light detector field.
In the prior art, patent CN102912300A discloses one kind and received without catalyst-assisted and vacuum thermal evaporation preparation SnS
The method of rice piece, its preparation method used is vacuum thermal evaporation, source material 1：1 Sn and S, substrate are ito glass, and it is lacked
Put and be that the molten boiling point of source material is different, while evaporate both materials to generate other products, such as SnS2And Sn2S3, cause to produce
Thing is impure, detail as per the accompanying drawing 1 in patent CN102912300A.In addition, the substrate of this method selection is ito glass, this
The temperature tolerance of kind substrate is relatively low, and the ITO layer on surface is the film particles of random deposition, and substrate flatness is relatively low, and
Orientation of particles is uneven, causes the direction of growth of the nanometer sheet of acquisition uncontrollable, detail as per in patent CN102912300A
Accompanying drawing 2 to 4.In contrast, selecting high-purity SnS, high temperature evaporation may insure the purity of source material to the present invention as source material
And unicity, and disproportionated reaction will not occur under the high temperature conditions for SnS, and pure thermal evaporation SnS is advantageous to prepare high-purity SnS
Single crystal nanoplate.Other substrate chooses resistant to elevated temperatures hexagonal structure single crystalline substrate, and surface is advantageous to the expansion of SnS planes without dangling bonds
Scattered length, form two-dimentional single crystal nanoplate.
Compared with prior art, in the present invention, applicant carries out preparing orthorhombic phase SnS two dimensions using physical vaporous deposition
Single crystal nanoplate, it is characterized in that using high-purity SnS powder as source material, fluorophologopite piece is substrate, and argon gas (Ar) is carrier gas,
Deposition 5-30 minutes obtain the orthorhombic phase SnS of large area, big domain on mica sheet under the conditions of 600-800 DEG C and 20-300Torr
Two-dimentional single crystal nanoplate.The SnS two dimensions single crystal nanoplate that the present invention prepares is brilliant in photo-detector, solar cell, field-effect
There is important researching value and wide application prospect in the fields such as body pipe.
Beneficial effects of the present invention are as follows：
(1) preparation technology is simple, and source material need to be only put into tube furnace by this experiment, be passed through carrier gas, set heating program
, a step pyroreaction can obtain orthorhombic phase SnS two dimension single crystal nanoplates；
(2) controllability is strong, and SnS nanometers can be efficiently controlled by changing the conditions such as reaction temperature, pressure, sedimentation time
The size of piece, thickness, uniformity etc.；
(3) repeatability is high, i.e., the success rate of the SnS two dimension single crystal nanoplates prepared in this way is high, therefore repeats
Property is preferable；
(4) synthesis cycle is short, and from heating, cooling samples this method to the end, it is only necessary to four or five hours, takes shorter；
(5) good crystallinity, because with high temperature thermal evaporation, the SnS two-dimensional nano pieces prepared on this condition have higher
Crystallinity and purity.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the synthesis schematic diagram of SnS two dimensions single crystal nanoplate of the present invention.
Fig. 2 shows the optical imagery (a) of SnS two dimension single crystal nanoplates prepared by the embodiment of the present invention 1, lateral dimension statistics
Scheme (b) and AFM (AFM) image and elevation information (c)；SnS two dimension monocrystalline prepared by the embodiment of the present invention 2 is received
The rice optical imagery (d) of piece, lateral dimension statistical chart (e) and AFM (AFM) image and elevation information (f)；This
Optical imagery (g), lateral dimension statistical chart (h) and the atomic force of SnS two dimension single crystal nanoplates prepared by inventive embodiments 3 show
Micro mirror (AFM) image and elevation information (i).
Fig. 3 shows X-ray diffraction (XRD) data spectrogram of SnS two dimension single crystal nanoplates prepared by the embodiment of the present invention 1.
Fig. 4 shows the Raman spectrogram of SnS two dimension single crystal nanoplates prepared by the embodiment of the present invention 1.
Fig. 5 shows transmission electron microscope (TEM) bright field image of single SnS two dimensions single crystal nanoplate prepared by the embodiment of the present invention 1
(a), corresponding SEAD (SAED) image (b), high-resolution TEM (HRTEM) images (c) and energy spectrum analysis (EDS)
Spectrogram (d).
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) preparation of fluorophologopite piece substrate：
1) mica sheet is cut into the small long square piece that size is 2cm*4cm using scissors.
2) it is with tapering tweezers that fluorophologopite piece is naturally cleaved into two pieces from centre, it is used as life by the use of the one side newly rived
Long substrate.
(2) fluorophologopite piece substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Claim
The high-purity SnS powder of amount 0.1g (purity is not less than 99%) is put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 80Torr in formula furnace chamber, and keeps argon gas flow velocity between 60sccm.
(4) diamond heating center is warming up to 600 DEG C, heating rate remains 20 DEG C/min, and the reaction time is 10 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, mica sheet substrate, Ke Yiguan are taken out
Observing mica sheet surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
Fig. 1 shows the synthesis schematic diagram of SnS two dimensions single crystal nanoplate of the present invention.The implication of each digitized representation is in figure：①-
Quartz ampoule, 2.-high-temperature resistant container, 3.-SnS powder, 4.-fluorophologopite piece, 5.-SnS two dimensions single crystal nanoplate.
(a) is the optical imagery of SnS two dimensions single crystal nanoplate manufactured in the present embodiment in Fig. 2, and (b) counts for lateral dimension
Figure, (c) is AFM (AFM) image and elevation information.
Fig. 3 shows X-ray diffraction (XRD) data spectrogram of SnS two dimension single crystal nanoplates prepared by the embodiment of the present invention 1.
In XRD spectrum in addition to 6 stronger diffraction maximums from mica sheet only only have a diffraction maximum, this diffraction peak in
At 32 °, corresponding to orthorhombic phase SnS (JCPDF No:39-0354, Pbnm) (040) crystal face, this shows that SnS nanometer sheets are tended to
Grown along [010] direction and using (010) crystal face as growth basal plane.
Fig. 4 shows the Raman spectrogram of SnS two dimension single crystal nanoplates prepared by the embodiment of the present invention 1.Feature in figure is drawn
Graceful peak AgAnd B3gThe nanometer sheet for proving to obtain is SnS.
Fig. 5 shows transmission electron microscope (TEM) bright field image of single SnS two dimensions single crystal nanoplate prepared by the embodiment of the present invention 1
(a), corresponding SEAD (SAED) image (b), high-resolution TEM (HRTEM) images (c) and energy spectrum analysis (EDS)
Spectrogram (d).SEAD (SAED) image has a set of two-dimentional rhombus diffraction spot, it was demonstrated that this nanometer sheet is orthorhombic phase
Monocrystalline.In high-resolution TEM (HRTEM) image (c), the interplanar distance that is identified in figure is 0.29nm, (101) with orthorhombic phase SnS
Crystal face is consistent.(d) energy spectrum analysis (EDS) shows this nanometer sheet sulfur-bearing and tin element, and two kinds of elements of wherein C and Cu come from copper
Net, illustration show that the atomic ratio of sulphur and tin is 1：1, it is SnS further to prove this nanometer sheet.
Embodiment 2
(1) preparation of fluorophologopite piece substrate：
1) mica sheet is cut into the small long square piece that size is 2cm*4cm using scissors.
2) it is with tapering tweezers that fluorophologopite piece is naturally cleaved into two pieces from centre, it is used as life by the use of the one side newly rived
Long substrate.
(2) fluorophologopite piece substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Claim
The high-purity SnS powder of amount 0.1g (purity is not less than 99%) is put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 80Torr in formula furnace chamber, and keeps argon gas flow velocity between 60sccm.
(4) diamond heating center is warming up to 700 DEG C, heating rate remains 20 DEG C/min, and the reaction time is 10 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, mica sheet substrate, Ke Yiguan are taken out
Observing mica sheet surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
(d) is the optical imagery of SnS two dimensions single crystal nanoplate manufactured in the present embodiment in Fig. 2, and (e) counts for lateral dimension
Figure, (f) is AFM (AFM) image and elevation information.
Embodiment 3
(1) preparation of fluorophologopite piece substrate：
1) mica sheet is cut into the small long square piece that size is 2cm*4cm using scissors.
2) it is with tapering tweezers that fluorophologopite piece is naturally cleaved into two pieces from centre, it is used as life by the use of the one side newly rived
Long substrate.
(2) fluorophologopite piece substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Claim
The high-purity SnS powder of amount 0.1g (purity is not less than 99%) is put into ceramic boat, then ceramic boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 300Torr in formula furnace chamber, and keeps argon gas flow velocity between 80sccm.
(4) diamond heating center is warming up to 800 DEG C, heating rate remains 20 DEG C/min, and the reaction time is 20 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, mica sheet substrate, Ke Yiguan are taken out
Observing mica sheet surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
(g) is the optical imagery of SnS two dimensions single crystal nanoplate manufactured in the present embodiment in Fig. 2, and (h) counts for lateral dimension
Figure, (i) is AFM (AFM) image and elevation information.Integrated embodiment 1-3,600 DEG C shown in Fig. 2 and
The optical imagery of the SnS two dimension single crystal nanoplates prepared under the conditions of 80Torr, 700 DEG C and 80Torr, 800 DEG C and 300Torr, table
The SnS nanometer sheets of bright acquisition all have two-dimensional structure.Corresponding 600 DEG C and 80Torr, 700 DEG C and 80Torr, 800 DEG C and
The lateral dimension statistical chart of the SnS two dimension single crystal nanoplates prepared under the conditions of 300Torr, show the sizes of SnS nanometer sheets with
The increase of temperature and pressure and become larger.And under the conditions of 600 DEG C and 80Torr, 700 DEG C and 80Torr, 800 DEG C and 300Torr
AFM (AFM) image and elevation information of the SnS single crystal nanoplates of preparation, illustrate the thickness of SnS nanometer sheets with
The increase of temperature and pressure and become larger.
Embodiment 4
(1) it is cleaned by ultrasonic 1cm*1cm Sapphire Substrate, nitrogen drying using acetone and deionized water；
(2) Sapphire Substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Weigh
The high-purity SnS powder of 0.2g (purity is not less than 99%) is put into quartz boat, then quartz boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 50Torr in formula furnace chamber, and keeps argon gas flow velocity between 180sccm.
(4) diamond heating center is warming up to 750 DEG C, heating rate remains 20 DEG C/min, and the reaction time is 20 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, substrate is taken out, it is observed that lining
Basal surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
Embodiment 5
(1) it is cleaned by ultrasonic 1cm*1cm Sapphire Substrate, nitrogen drying using acetone and deionized water：
(2) Sapphire Substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Weigh
The high-purity SnS powder of 0.15g (purity is not less than 99%) is put into corundum boat, then corundum boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 30Torr in formula furnace chamber, and keeps argon gas flow velocity between 200sccm.
(4) diamond heating center is warming up to 650 DEG C, heating rate remains 20 DEG C/min, and the reaction time is 15 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, substrate is taken out, it is observed that lining
Basal surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
Embodiment 6
(1) it is cleaned by ultrasonic 1cm*1cm Sapphire Substrate, nitrogen drying using acetone and deionized water：
(2) Sapphire Substrate is put in diamond heating center downstream successively, apart from heating source center 8-20cm.Weigh
The high-purity SnS powder of 0.3g (purity is not less than 99%) is put into corundum boat, then corundum boat is placed in the heating zone of tube furnace.
(3) open mechanical pump to be vacuumized, when tube furnace intracavitary pressure is down to 0.1Pa, being filled with high-purity argon gas makes pipe
Pressure returns to 250Torr in formula furnace chamber, and keeps argon gas flow velocity between 20sccm.
(4) diamond heating center is warming up to 800 DEG C, heating rate remains 10 DEG C/min, and the reaction time is 25 points
Clock.
(5) after reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, substrate is taken out, it is observed that lining
Basal surface has grayish thin film, that is, the SnS two dimension single crystal nanoplates prepared.
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 (6)
- A kind of 1. method of controllable preparation orthorhombic phase stannous sulfide two dimension single crystal nanoplate, it is characterised in that methods described includes Following steps：1）Choose with growth substrates of the smooth substrate of atomically flating as SnS；2）Substrate is placed in the heated center downstream of horizontal pipe furnace, apart from heated center 8-20cm, SnS powder is put into resistance to height In warm container, high-temperature resistant container is placed in the heated center of horizontal pipe furnace；3）To tubular type stove evacuation, when pressure is down to 0.1Pa in stove, being filled with inactive gas returns to tube furnace intracavitary pressure 20-300Torr, and inactive gas flow velocity is kept between 20-200sccm；4）Horizontal pipe furnace heated center is warming up to 600-800 DEG C, between heating rate remains 5-20 DEG C/min, the reaction time For 5-30 minutes；5）After reaction terminates, after tubular type furnace chamber temperature Temperature fall to room temperature, substrate is taken out, substrate surface grows SnS Two-dimentional single crystal nanoplate.
- 2. the method for controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates according to claim 1, it is characterised in that：Step Rapid 1）In, the substrate is mica sheet or sapphire.
- 3. the method for controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates according to claim 2, it is characterised in that：Step Rapid 1）In, the substrate is fluorophologopite piece, and fluorophologopite piece is naturally cleaved into two thin slices from centre, chooses new cleavage Face is as aufwuchsplate.
- 4. the method for controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates according to claim 1, it is characterised in that：Step Rapid 2）In, the SnS powder is high-purity SnS powder, and purity is not less than 99%.
- 5. the method for controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates according to claim 1, it is characterised in that：Step Rapid 2）In, the high-temperature resistant container is ceramic boat, corundum boat or quartz boat.
- 6. the method for controllable preparation orthorhombic phase SnS two dimension single crystal nanoplates according to claim 1, it is characterised in that：Step Rapid 3）In, the inactive gas is nitrogen, helium or neon.
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| CN108842184A (en) * | 2018-06-27 | 2018-11-20 | 北京航空航天大学 | A kind of p-type SnS monocrystal material and preparation method thereof |
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| CN111416032B (en) * | 2019-01-08 | 2022-02-18 | 北京航空航天大学 | N-type SnS single crystal thermoelectric material and preparation method thereof |
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| CN114477270B (en) * | 2022-02-21 | 2023-10-27 | 福建师范大学 | Method for growing ultrathin stannous sulfide nanosheets by sulfur passivation |
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