CN102912300A - 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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- CN102912300A CN102912300A CN2012104391908A CN201210439190A CN102912300A CN 102912300 A CN102912300 A CN 102912300A CN 2012104391908 A CN2012104391908 A CN 2012104391908A CN 201210439190 A CN201210439190 A CN 201210439190A CN 102912300 A CN102912300 A CN 102912300A
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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 the nanostructure growth field, is a kind of in the auxiliary lower method with Vacuum sublimation growth SnS nanometer sheet of catalyst-free.
Background technology
SnS is a kind of IV-VI family semi-conductor, and its direct band gap is wide to be 1.2～1.5eV, and indirect band gap is wide to be 1.0～1.1eV, and very near the best energy gap 1.5eV of solar cell, 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, taps a new source of energy, and the environment of preserving our planet is compeled at the tip of the brow, therefore, greatly develops heliotechnics, and the efficiency of conversion that improves 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 of a large amount of preparation solar cells.The SnS nanostructure that preparation is novel, it is significant to improve photoelectric transformation efficiency.
At present, the preparation method about the 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): such as 2006, the people such as Subhendu K are take tinfoil paper as the source, water and ethanol clean and descend heating after 20 minutes at 100 ℃, immerse the aqueous solution of CETRIMIDE POWDER, be exposed to again in the H2S atmosphere after 12 hours, at the tinfoil paper Surface Creation SnS nano wire of grey black.Consult Crystal Growth ﹠amp; Design the 6th volume 2177-2181 page or leaf.
Electrochemical deposition method (electrochemical deposition): such as 2009, the people such as G.H.Yue with saturated calomel electrode as the reference electrode, with the alumina formwork of aluminium substrate as working electrode, the platinized platinum conduct is to electrode, keeping the temperature of solution is 10 ℃, deposits after 5 minutes, with pure water sample is cleaned, then dry under field conditions (factors), obtain monocrystalline SnS nano-wire array.Consult Nanoscale Research Letters the 4th volume 359-363 page or leaf.
Molten salt solvent method (molten salt solvent method): such as 2012, the people such as Hulin Zhang were with the LiNO of 6g
3And KNO
3Mixture is inserted in the reactor of 25ml, adds 0.1mmol SnCl again
22H
2O, the hydrazine hydrate of 0.1mmol thiocarbamide and 5ml is sealed in 200 ℃ and kept 24 hours, again cool to room temperature under physical environment.At last, sample inserted in deionized water, the ethanol clean, 60 ℃ of airings 2 hours have obtained the SnS nano belt.Consult Journal of Alloys and Compounds the 513rd volume 1-5 page or leaf.
Vapor transportation method (vapor transport method): such as 2009, the people such as M.Devika were evaporated high-purity SnS powder under the condition of high vacuum, by the control growth temperature, highly, that growth time, sedimentation rate obtain SnS is nanocrystalline.Draw best growth conditions and be T～150 ℃, h=14cm, t～1h, RD=0.2nm/s.Consult Applied Physics Letters the 95th volume 261907-261909 page or leaf.
Wet chemistry method (wet chemical route): such 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, and SnCl wherein
2.2H
2O and Na
2The stoichiometric ratio of S is 1: 3.Under the condition of not adding any other tensio-active agent, in the time of 80 ℃, with SnCl
2.2H
2O solution dropwise joins Na
2In the S solution, the particle that will obtain after then will reacting separates also successively spent glycol, alcohol wash with whizzer, at room temperature dries again, and obtaining product is the SnS nanometer sheet.Consult Materials Letters the 65th volume 1148-1150 page or leaf.
Chemical Vapor deposition process (chemical vapor deposition): such as 2012, the people such as G.H.Yue utilize the auxiliary chemical Vapor deposition process of catalyzer, take SnS, S as the source, the ito glass that is coated with gold nano grain is substrate, 800 ℃ of lower maintenances 15 minutes, pass into simultaneously high-purity Ar and H2, synthesized the SnS nano wire.Consult Applied Physics A the 106th volume 87-91 page or leaf.
Except above these methods, closely Vacuum sublimation also is a kind of method for preparing nanostructure commonly used, and Vacuum sublimation is a kind of relatively traditional method, technique is simple, easy to operate, sedimentation rate is high, be beneficial to the big area preparing product, low, the non-environmental-pollution of cost, in industrial production very large potentiality is arranged.
Summary of the invention
The object of the present invention is to provide the method for the auxiliary vacuum thermal evaporation growth SnS nanometer sheet of a kind of catalyst-free.
The present invention realizes by following technological process:
After S powder (99.99%) and metal Sn bits (99.99%) are carried out weighing by the proportioning of 1mol: 1mol, S powder and Sn bits successively are positioned in the resistive heating boat that molybdenum sheet makes as evaporation source (the heating boat is fixed on the copper electrode in the vacuum-evaporation stove), place ito glass as substrate to 1.1 centimeters for 0.9 centimetre above evaporation source, vacuum tightness reaches 1.8 * 10 in vapourizing furnace
-2Pa～2.0 * 10
-2Behind the Pa, the speed increase electric current with 3.3A/min when evaporation current reaches about 130A, keeps about 15 minutes (the whole process middle bell jar is connected with recirculated cooling water), and the grey black settling that finally obtains at substrate is the SnS sample.
Compared with prior art, characteristics of the present invention are: experimental technique is simple, easy to operate, catalyst-free auxiliary, and the pattern controllability is good, and cost is low, and output is large, and environment without harm, therefore is fit to industrial mass production.
Description of drawings
Fig. 1, Fig. 5, Fig. 9 are respectively the XRD figure spectrum of embodiment 1,2,3 products, the diffraction peak of () expression product S nS among the figure, the diffraction peak of expression 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
Adopting high-purity Sn bits (99.99%) and high-purity S powder (99.99%) is raw material, both press 1mol: after the weighing of 1mol proportioning, the Sn bits are positioned in the resistive heating boat of molybdenum sheet making, place again the S powder thereon as evaporation source, place about 1.0cm place, evaporation source top with ito glass as substrate, airtight evaporation cavity is when vacuum tightness reaches 1.8 * 10
-2Behind the Pa, the speed increase electric current with 3.3A/min makes electric current increase to gradually 130A, keeps 15 minutes (the whole process middle bell jar is connected with recirculated cooling water), at substrate surface the grey black settling is arranged.
As shown in Figure 1, be the XRD figure of products therefrom 1.The result shows that products therefrom is the SnS of rhombic system, and its diffraction peak conforms to the PDF#79-2193 card; It can also be seen that from spectrogram product is along (112) direction preferential growth.In addition, also have the diffraction peak of S, come from unreacted S powder.
Such as Fig. 2, Fig. 3, shown in Figure 4, products therefrom 1 is nanometer sheet, thick about 80 nanometers of nanometer sheet.
Adopting high-purity Sn bits (99.99%) and high-purity S powder (99.99%) is raw material, both press 1mol: after the weighing of 1mol proportioning, the S powder is positioned in the resistive heating boat of molybdenum sheet making, place again the Sn bits thereon as evaporation source, place about 0.9cm place, evaporation source top with ito glass as substrate, airtight evaporation cavity is when vacuum tightness reaches 2.0 * 10
-2Behind the Pa, the speed increase electric current with 3.3A/min makes electric current increase to gradually 130A, keeps 15 minutes (the whole process middle bell jar is connected with recirculated cooling water), at substrate surface the grey black settling is arranged.
As shown in Figure 5, be the XRD figure of products therefrom 2.The result shows that products therefrom is the SnS of rhombic system, and its diffraction peak conforms to the PDF#33-1375 card; It can also be seen that from spectrogram product is along (002) direction preferential growth.In addition, also have the diffraction peak of S, come from unreacted S powder.
Such as Fig. 6, Fig. 7, shown in Figure 8, products therefrom 2 is nanometer sheet, thick about tens nanometers of nanometer sheet.
Embodiment 3
Adopting high-purity Sn bits (99.99%) and high-purity S powder (99.99%) is raw material, both press 1mol: after the weighing of 1mol proportioning, the S powder is positioned in the resistive heating boat of molybdenum sheet making, place again the Sn bits thereon as evaporation source, place about 1.1cm place, evaporation source top with ito glass as substrate, airtight evaporation cavity is when vacuum tightness reaches 2.0 * 10
-2Pa, the speed increase electric current with 3.3A/min makes electric current increase to gradually 130A, keeps 15 minutes (the whole process middle bell jar is connected with recirculated cooling water), at substrate surface the grey black settling is arranged.
As shown in Figure 9, be the XRD figure of products therefrom 3.The result shows that products therefrom is the SnS of rhombic system, and its diffraction peak conforms to the PDF#33-1375 card; It can also be seen that from spectrogram product is along (101) direction preferential growth.In addition, also have the diffraction peak of S, come from unreacted S powder.
Such as Figure 10, shown in Figure 11, products therefrom 3 is nanometer sheet, and interlaced connection is " flower " shape structure, thick about tens nanometers of nanometer sheet.
Claims (3)
1. the invention discloses the method that the thermal evaporation of a kind of catalyst-free assisted vacuum prepares the SnS nanometer sheet, it is characterized in that realizing by following technological process: according to 1: 1 mol ratio S powder and metal Sn are considered to be worth doing, be placed on first in the resistive heating boat of doing with molybdenum sheet as evaporation source, the heating boat places in the vacuum-evaporation stove, the ITO substrate places 0.9 centimetre of evaporation source top to 1.1 centimeters, and vacuum tightness reaches 1.8 * 10 in vapourizing furnace
-2Pa～2.0 * 10
-2Pa when heating current is 130A, kept 15 minutes, and the grey black settling in that substrate forms is the SnS nanometer sheet.
2. the method for claim 1 is characterized in that, and is auxiliary without any catalyzer in the process of preparation SnS nanometer sheet.
3. the method for claim 1 is characterized in that, prepared product SnS nanometer sheet pattern homogeneous, and output is large.
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Cited By (3)
| 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 method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet |
| 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 |
| CN109179489A (en) * | 2018-10-26 | 2019-01-11 | 浙江大学 | The preparation method and product of a kind of two-dimensional ultrathin stannous sulfide nanometer sheet and application |
Citations (2)
| 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 |
| CN101894877A (en) * | 2009-05-22 | 2010-11-24 | 伍丽 | Method for preparing stannous sulfide thin film solar cell |
-
2012
- 2012-11-07 CN CN201210439190.8A patent/CN102912300B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
| CN101894877A (en) * | 2009-05-22 | 2010-11-24 | 伍丽 | Method for preparing stannous sulfide thin film solar cell |
Non-Patent Citations (3)
| Title |
|---|
| HIDENORI NOGUCHI ETAL.: "Characterization of vacuum-evaporated tin sulfide film for solar cell materials", 《 SOLAR ENERGY MATERIALS AND SOLAR CELLS》 * |
| 邱永华等: "真空蒸发法制备SnS薄膜及其光电性能研究", 《光电子•激光》 * |
| 邱永华等: "真空蒸发法制备SnS薄膜及其光电性能研究", 《光电子•激光》, vol. 17, no. 7, 31 July 2006 (2006-07-31), pages 817 - 820 * |
Cited By (3)
| 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 method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet |
| 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 |
| CN109179489A (en) * | 2018-10-26 | 2019-01-11 | 浙江大学 | The preparation method and product of a kind of two-dimensional ultrathin stannous sulfide nanometer sheet and application |
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