CN102912300B - Method for preparing SnS nanosheet by means of vacuum thermal evaporation without assistance of catalyst - Google Patents
Method for preparing SnS nanosheet by means of vacuum thermal evaporation without assistance of catalyst Download PDFInfo
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- CN102912300B CN102912300B CN201210439190.8A CN201210439190A CN102912300B CN 102912300 B CN102912300 B CN 102912300B CN 201210439190 A CN201210439190 A CN 201210439190A CN 102912300 B CN102912300 B CN 102912300B
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Abstract
The invention discloses a method for preparing a SnS nanosheet by means of vacuum thermal evaporation without assistance of a catalyst. The method is realized through the following technical process: preparing S powder and Sn metal fillings in proportion of 1 mol: 1 mol; successively placing the S powder and the Sn metal fillings in a resistance heating boat made of molybdenum sheets to serve as evaporation sources; placing an ITO glass substrate at a position 0.9cm-1.1cm above the boat; hermetically enclosing a vaporizing furnace; when the vacuum degree of the vacuum vaporizing furnace reaches 1.8*10<-2> Pa - 2.0*10<-2> Pa and the heating current reaches 130A, keeping for 15 minutes to obtain the SnS nanosheet. The method has the characteristics of uniform shape of the obtained SnS nanosheet, high yield, no catalyst, simple preparation method, facilitation of popularization, and suitability for large-scale industrial production.
Description
Technical field
The invention belongs to nanostructure growth field, is a kind of method growing SnS nanometer sheet under catalyst-free is assisted with Vacuum sublimation.
Background technology
SnS is a kind of group IV-VI semi-conductor, and its direct band gap is wide is 1.2 ~ 1.5eV, and indirect belt gap length is 1.0 ~ 1.1eV, closely the best energy gap 1.5eV of solar cell, and optical absorption coefficient is greater than 10
4cm
-1, its effciency of energy transfer can reach 25% in theory.Along with the development of economic society, the energy becomes the bottleneck problem of restriction human social development day by day, and tap a new source of energy, environment of preserving our planet is compeled at the tip of the brow, therefore, greatly develops heliotechnics, and the efficiency of conversion improving solar cell has very important meaning.SnS is a kind of pollution-free, non-toxic material, and the content of Sn and S is all very abundant on earth, meets the requirement preparing solar cell in a large number.The SnS nanostructure that preparation is novel, improves photoelectric transformation efficiency significant.
At present, the preparation method about SnS nanostructure has a lot: gas-solid reaction method (gas-solid reaction), electrochemical deposition method (electrochemical deposition), molten salt solvent method (molten salt solvent method), vapor transportation method (vapor transport method), wet chemistry method (wet chemical route), chemical Vapor deposition process (chemical vapor deposition) etc.
Gas-solid reaction method (gas-solid reaction): as 2006, the people such as Subhendu K take tinfoil paper as source, heat with water and ethanol purge and at 100 DEG C after 20 minutes, immerse the aqueous solution of CETRIMIDE POWDER, be exposed in H2S atmosphere after 12 hours again, the SnS nano wire of grey black at tinfoil paper Surface Creation.Consult Crystal Growth & Design the 6th volume 2177-2181 page.
Electrochemical deposition method (electrochemical deposition): as 2009, the people such as G.H.Yue are using saturated calomel electrode as reference electrode, with the alumina formwork of aluminium substrate as working electrode, platinized platinum is as to electrode, the temperature keeping solution is 10 DEG C, deposits after 5 minutes, cleans with pure water to sample, then dry under field conditions (factors), obtain monocrystalline SnS nano-wire array.Consult Nanoscale Research Letters the 4th volume 359-363 page.
Molten salt solvent method (molten salt solvent method): as 2012, the people such as Hulin Zhang were by the LiNO of 6g
3and KNO
3mixture is inserted in the reactor of 25ml, then adds 0.1mmol SnCl
22H
2the hydrazine hydrate of O, 0.1mmol thiocarbamide and 5ml, be sealed in 200 DEG C keep 24 hours, then under physical environment cool to room temperature.Finally, inserted by sample in deionized water, ethanol and clean, 60 DEG C of airings 2 hours, obtain SnS nano belt.Consult Journal of Alloys and Compounds the 513rd volume 1-5 page.
Vapor transportation method (vapor transport method): as 2009, the people such as M.Devika evaporated high-purity SnS powder under the condition of high vacuum, by controlling growth temperature, highly, SnS is nanocrystalline for the acquisition of growth time, sedimentation rate.Show that best growth conditions is T ~ 150 DEG C, h=14cm, t ~ 1h, RD=0.2nm/s.Consult Applied Physics Letters the 95th volume 261907-261909 page.
Wet chemistry method (wet chemical route): as 2011, the people such as S.Sohila were with SnCl
2.2H
2o and Na
2s is respectively Xi Yuan and sulphur source, take ethylene glycol as solvent, wherein SnCl
2.2H
2o and Na
2the stoichiometric ratio of S is 1: 3.Under the condition of not adding other tensio-active agent any, 80 DEG C time, by SnCl
2.2H
2o dropwise joins Na
2in S solution, be then separated and priority spent glycol, alcohol washes by the particle whizzer obtained after reaction, more at room temperature dry, obtaining product is SnS nanometer sheet.Consult Materials Letters the 65th volume 1148-1150 page.
Chemical Vapor deposition process (chemical vapor deposition): as 2012, the chemical Vapor deposition process that the people such as G.H.Yue utilize catalyzer auxiliary, with SnS, S for source, the ito glass being coated with gold nano grain is substrate, keep 15 minutes at 800 DEG C, pass into high-purity Ar and H2 simultaneously, synthesize SnS nano wire.Consult Applied Physics A the 106th volume 87-91 page.
Except these methods above, closely Vacuum sublimation is also a kind of conventional method preparing nanostructure, and Vacuum sublimation is a kind of relatively traditional method, technique is simple, easy to operate, sedimentation rate is high, be beneficial to big area preparing product, cost is low, non-environmental-pollution, and industrial production has very large potentiality.
Summary of the invention
The method of the vacuum thermal evaporation growth SnS nanometer sheet that the object of the present invention is to provide a kind of catalyst-free to assist.
The present invention is realized by following technological process:
S powder (99.99%) and metal Sn are considered to be worth doing (99.99%) by 1mol: 1mol proportioning weigh after, S powder and Sn bits are successively positioned in the resistive heating boat that molybdenum sheet makes as evaporation source (heating boat is fixed on the copper electrode in vacuum-evaporation stove), ito glass is placed as substrate, when in vapourizing furnace, vacuum tightness reaches 1.8 × 10 to 1.1 centimeters for 0.9 centimetre above evaporation source
-2pa ~ 2.0 × 10
-2after Pa, increase electric current with the speed of 3.3A/min, when evaporation current reaches about 130A, keep about 15 minutes (whole process middle bell jar is connected with recirculated cooling water), the grey black settling finally obtained on substrate, is SnS sample.
Compared with prior art, feature of the present invention is: experimental technique is simple, easy to operate, catalyst-free is assisted, and morphology controllable is good, and cost is low, and output is large, to environment without harm, is therefore applicable to industrial mass production.
Accompanying drawing explanation
Fig. 1, Fig. 5, Fig. 9 are respectively the XRD figure spectrum of embodiment 1,2,3 product, and in figure, () represents the diffraction peak of product S nS, represents the diffraction peak of S.
Fig. 2 ~ 4 are the scanning electron microscope diagram sheet of embodiment 1 sample different amplification.
Fig. 6 ~ 8 are the scanning electron microscope diagram sheet of embodiment 2 sample different amplification.
Figure 10 ~ 11 are the scanning electron microscope diagram sheet of embodiment 3 sample different amplification.
Embodiment
Embodiment 1
High-purity Sn bits (99.99%) and high-purity S powder (99.99%) is adopted to be raw material, after both press 1mol: 1mol proportioning weighing, Sn bits are positioned in the resistive heating boat of molybdenum sheet making, place S powder more thereon as evaporation source, about 1.0cm place above evaporation source is placed in using ito glass as substrate, airtight evaporation cavity, when vacuum tightness reaches 1.8 × 10
-2after Pa, increase electric current with the speed of 3.3A/min, make electric current be increased to 130A gradually, keep 15 minutes (whole process middle bell jar is connected with recirculated cooling water), have grey black settling at substrate surface.
As shown in Figure 1, be the XRD figure of products therefrom 1.Result display products therefrom is the SnS of rhombic system, and its diffraction peak conforms to PDF#79-2193 card; It can also be seen that product is along (112) direction preferential growth from spectrogram.In addition, also have the diffraction peak of S, come from unreacted S powder.
As shown in Figure 2, Figure 3, Figure 4, products therefrom 1 is nanometer sheet, thick about 80 nanometers of nanometer sheet.
Embodiment 2
High-purity Sn bits (99.99%) and high-purity S powder (99.99%) is adopted to be raw material, after both press 1mol: 1mol proportioning weighing, S powder is positioned in the resistive heating boat of molybdenum sheet making, place Sn bits more thereon as evaporation source, about 0.9cm place above evaporation source is placed in using ito glass as substrate, airtight evaporation cavity, when vacuum tightness reaches 2.0 × 10
-2after Pa, increase electric current with the speed of 3.3A/min, make electric current be increased to 130A gradually, keep 15 minutes (whole process middle bell jar is connected with recirculated cooling water), have grey black settling at substrate surface.
As shown in Figure 5, be the XRD figure of products therefrom 2.Result display products therefrom is the SnS of rhombic system, and its diffraction peak conforms to PDF#33-1375 card; It can also be seen that product is along (002) direction preferential growth from spectrogram.In addition, also have the diffraction peak of S, come from unreacted S powder.
As shown in Fig. 6, Fig. 7, Fig. 8, products therefrom 2 is nanometer sheet, thick about tens nanometers of nanometer sheet.
Embodiment 3
High-purity Sn bits (99.99%) and high-purity S powder (99.99%) is adopted to be raw material, after both press 1mol: 1mol proportioning weighing, S powder is positioned in the resistive heating boat of molybdenum sheet making, place Sn bits more thereon as evaporation source, about 1.1cm place above evaporation source is placed in using ito glass as substrate, airtight evaporation cavity, when vacuum tightness reaches 2.0 × 10
-2pa, increases electric current with the speed of 3.3A/min, makes electric current be increased to 130A gradually, keep 15 minutes (whole process middle bell jar is connected with recirculated cooling water), have grey black settling at substrate surface.
As shown in Figure 9, be the XRD figure of products therefrom 3.Result display products therefrom is the SnS of rhombic system, and its diffraction peak conforms to PDF#33-1375 card; It can also be seen that product is along (101) direction preferential growth from spectrogram.In addition, also have the diffraction peak of S, come from unreacted S powder.
As shown in Figure 10, Figure 11, products therefrom 3 is nanometer sheet, and interlaced connection is in " flower " shape structure, thick about tens nanometers of nanometer sheet.
Claims (3)
1. the method for SnS nanometer sheet is prepared in catalyst-free assisted vacuum thermal evaporation, it is characterized in that being realized by following technological process: S powder and metal Sn are considered to be worth doing by the mol ratio according to 1: 1, first be placed in the resistive heating boat done using molybdenum sheet as evaporation source, heating boat is placed in vacuum-evaporation stove, ITO substrate to be placed in above evaporation source 0.9 centimetre to 1.1 centimeters, when in vapourizing furnace, vacuum tightness reaches 1.8 × 10
-2pa ~ 2.0 × 10
-2pa, when heating current is 130A, keep 15 minutes, the grey black settling that substrate is formed, is SnS nanometer sheet.
2. the method for claim 1, is characterized in that, assists in the process of preparation SnS nanometer sheet without any catalyzer.
3. the method for claim 1, is characterized in that, obtained product SnS nanometer sheet pattern is homogeneous.
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| CN102912300B true CN102912300B (en) | 2015-01-14 |
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| CN105551946A (en) * | 2016-01-07 | 2016-05-04 | 广东工业大学 | Preparation method for stannous sulfide nanosheet and photoelectric detector prepared based on stannous sulfide nanosheet |
| CN105420815B (en) * | 2016-01-07 | 2018-01-30 | 中国科学院理化技术研究所 | A kind of method of controllable preparation orthorhombic phase stannous sulfide two dimension single crystal nanoplate |
| CN109179489B (en) * | 2018-10-26 | 2020-07-24 | 浙江大学 | Preparation method, product and application of two-dimensional ultrathin stannous sulfide nanosheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894877A (en) * | 2009-05-22 | 2010-11-24 | 伍丽 | Method for preparing stannous sulfide thin film solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08144044A (en) * | 1994-11-18 | 1996-06-04 | Nisshin Steel Co Ltd | Production of tin sulfide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894877A (en) * | 2009-05-22 | 2010-11-24 | 伍丽 | Method for preparing stannous sulfide thin film solar cell |
Non-Patent Citations (3)
| Title |
|---|
| Characterization of vacuum-evaporated tin sulfide film for solar cell materials;Hidenori Noguchi etal.;《 Solar Energy Materials and Solar cells》;19941231(第35期);第325－331页 * |
| JP特开平8-144044A 1996.06.04 * |
| 真空蒸发法制备SnS薄膜及其光电性能研究;邱永华等;《光电子•激光》;20060731;第17卷(第7期);第817－820页 * |
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