CN105253910A - Method for one-step synthesis of large-size SnS nanoflake - Google Patents

Method for one-step synthesis of large-size SnS nanoflake Download PDF

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Publication number
CN105253910A
CN105253910A CN201510589741.2A CN201510589741A CN105253910A CN 105253910 A CN105253910 A CN 105253910A CN 201510589741 A CN201510589741 A CN 201510589741A CN 105253910 A CN105253910 A CN 105253910A
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sns
nanoflake
temperature
preparation
minutes
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CN105253910B (en
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曹萌
高王升
张庆
王林军
沈悦
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The invention discloses a low-cost high-quality method for one-step synthesis of a large-size SnS nanoflake. The method comprises the following steps: successively adding a magnetic stirring bar and a certain amount of reactant precursors consisting of stannous chloride, powdered sulfur and oleylamine into a four-necked flask, fixing the four-necked flask on a constant-temperature magnetic stirrer and after installation of the stirrer, starting a rotor for stirring and introducing Ar gas, wherein gas flow may be great; allowing a temperature to rise to 70 DEG C, waiting for 30 min, then allowing the temperature to rise to 180 DEG C and reducing Ar gas flow at the same time, allowing the temperature to rise to 300 DEG C after 30 min and then allowing the temperature to drop to 50 DEG C; and stopping heating and magnetic stirring, taking out a sample, cleaning the sample a plurality of times with toluene and absolute ethyl alcohol as cleaning compounds and collecting a sediment at a lower layer so as to obtain the large-size SnS nanoflake. The invention has the following advantages: the preparation method is simple and has low cost; material sources of the precursors are rich; the nanoflake is suitable for synthesis in batch; and the nanoflake has a large diameter and good morphology, substantially reduce compounding of carriers in a crystal boundary area and assists preparation of absorption layers with uniform thickness for solar battery devices to a certain extent.

Description

The preparation method of one-step synthesis large size SnS nanometer sheet
Technical field
The present invention relates to a kind of preparation technology that can be used as the group IV-VI semiconductor nano sheet of film photovoltaic cell light absorbing zone, also relate to a kind of method of morphology control of associated materials.
Background technology
In recent years, photovoltaic material is more and more concerned by people, and especially the historical breakthrough of photovoltaic material created by crystalline silicon material and CIGS thin-film material.But because crystalline silicon involves great expense, copper-indium-galliun-selenium mostly is rare element on the earth, so be badly in need of a kind of earth rich reserves, the recovery material that cheap, making method is simply new to complete this mission.
SnS is a kind of than better suited photovoltaic material, and its optics direct band gap width is 1.2 ~ 1.5eV, and optics indirect band gap width is 1.0 ~ 1.1eV, just in time has good Spectral matching with solar radiation, so be suitable for use in very much the absorption layer of photovoltaic cell.In addition, in the near infrared detector and photovoltage device of electroluminescent display, SnS material has and applies very widely.SnS nano material has and is made into various microtexture, as nanocrystalline in nano belt, sea urchin shape nanocrystalline, random profile thin slice etc.But temporarily also do not occur that one utilizes the better larger-size nanometer sheet structure of thermochemical method one-step synthesis pattern, adopt constant temperature blender with magnetic force as well heater, four neck flasks are reaction vessel, control Heating temperature and time well, not needing to add high pressure does not need to vacuumize, equipment is simple, with low cost, and the sheet-like morphology of product is better.
Summary of the invention
The object of this invention is to provide the preparation method of large size SnS nanometer sheet of a kind of low cost, high quality one-step synthesis, this preparation method operation is comparatively simple, raw material is cheap and be all the macroelement wide material sources of the earth, the SnS crystal prepared is all sheet structure, and sheet thickness is Nano grade, the diameter of sheet is at several microns to 10 microns, and sheet structure is even, better dispersed.
Preparation method's following steps of large size SnS nanometer sheet in the present invention:
Successively by magnetic stir bar, reactant presoma 0.48mmolSnCl 22H 2o, 0.58mmolS, 8ml oleyl amine adds in the four neck flasks of a 100ml, is fixed in constant temperature blender with magnetic force by flask, and makes rotor keep rotating with the rotating speed of 500 turns/min, load onto condensing works, thermopair, thermometer, passes into Ar gas, air-flow can be slightly large, 70 DEG C time, keep 30 minutes, rear reduction air-flow, be warming up to 180 DEG C and keep 30 minutes, be warming up to 280 DEG C ~ 300 DEG C again to keep 30 minutes, then be cooled to room temperature.Then use toluene and dehydrated alcohol as clean-out system by cooled reactant with the centrifugation 3 minutes of 12000 revs/min, and repeatedly until the clarification of upper strata centrifugal solution, collect lower sediment thing, obtain large size SnS nanometer sheet.
The invention has the advantages that: the preparation method of nanometer sheet is simple, and cost is lower, and persursor material used is with low cost, be applicable to batch synthesis.The diameter of nanometer sheet is all at 5 ~ 10 μm, and the compound of a large amount of minimizing current carriers in grain boundary area, can provide certain help for the absorption layer preparing thickness even solar cell device.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Fig. 1 is the X ray diffracting spectrum of large size SnS nanometer sheet of the present invention.
Fig. 2 is the scanning electron microscope collection of illustrative plates of large size SnS nanometer sheet of the present invention.
Fig. 3 is that the EDS of large size SnS nanometer sheet of the present invention can spectrogram.
Embodiment
Provide preferred embodiment of the present invention below, enablely understand process of the present invention better.
embodiment 1
Successively by magnetic stir bar, reactant presoma 0.48mmolSnCl 22H 2o, 0.58mmolS, 8ml oleyl amine adds in the four neck flasks of a 100ml, is fixed in constant temperature blender with magnetic force by flask, and makes rotor keep rotating with the rotating speed of 500 turns/min, load onto condensing works, thermopair, thermometer, passes into Ar gas, air-flow can be slightly large, 70 DEG C time, keep 30 minutes, rear reduction air-flow, be warming up to 180 DEG C and keep 30 minutes, be warming up to 280 DEG C ~ 300 DEG C again to keep 30 minutes, then be cooled to room temperature.Then use toluene and dehydrated alcohol as clean-out system by cooled reactant with the centrifugation 3 minutes of 12000 revs/min, and repeatedly until the clarification of upper strata centrifugal solution, collect lower sediment thing, obtain large size SnS nanometer sheet.Be dispersed in finally precipitating in toluene.
the explanation explanation of instrument test gained accompanying drawing for the present invention
The diffraction peak (110) marked in Fig. 1, (120), (021), (101), (111), (040), (131), (141), (150), (211), (151), (160), (061), (042), (251), (080) corresponding respectively angle of diffraction is 21.96 °, 25.96 °, 27.38 °, 30.38 °, 31.48 °, 31.92 °, 38.96 °, 44.7 °, 45.48 °, 48.52 °, 51.26 °, 53.36 ° 54.26 °, 56.66 °, 64.18 °, 66.8 °, mate completely with the diffraction peak of SnS in the PDF card (14-0620) of standard, and without any assorted peak, find out that obtained is the SnS of pure phase thus.
Can find out a large amount of flaky nanometer structure in Fig. 2, and the diameter of its sheet structure is all at 5 ~ 10 microns, size is comparatively large, better dispersed.
As can be seen from Figure 3, the peak position of other independent elements do not measured by energy spectrometer, shows the impurity not having other element, is all SnS.Again as can be seen from Table 1, Sn element and S Elements Atom per-cent are substantially close to 1 to 1, and what show generation is the large size SnS nanometer sheet comparing pure phase.
。

Claims (3)

1. a preparation method for one-step synthesis large size SnS nanometer sheet, is characterized in that having following process and step:
A. successively by magnetic stir bar, reactant presoma 0.48mmolSnCl 22H 2o, 0.58mmolS, 8ml oleyl amine adds in the four neck flasks of a 100ml, is fixed in constant temperature blender with magnetic force by flask, and makes rotor keep rotating with the rotating speed of 500 turns/min;
B. load onto condensing works, thermopair, thermometer, pass into Ar gas, 70 DEG C time, keep 30 minutes, rear reduction air-flow, be warming up to 180 DEG C and keep 30 minutes, then be warming up to 280 DEG C ~ 300 DEG C maintenances 30 minutes, then be cooled to room temperature;
C. then use toluene and dehydrated alcohol as clean-out system by cooled reactant with the centrifugation 3 minutes of 12000 revs/min, and repeatedly until the clarification of upper strata centrifugal solution, collect lower sediment thing, obtain large size SnS nanometer sheet.
2. require the preparation method of described a kind of one-step synthesis large size SnS nanometer sheet according to right 1, it is characterized in that: described reactant presoma tin protochloride stannous acetate replaces.
3. require the preparation method of described a kind of one-step synthesis large size SnS nanometer sheet according to right 1, it is characterized in that: described reactant presoma sulphur powder Dodecyl Mercaptan replaces.
CN201510589741.2A 2015-09-17 2015-09-17 The preparation method of one-step synthesis large scale SnS nanometer sheets Expired - Fee Related CN105253910B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106115772A (en) * 2016-03-26 2016-11-16 上海大学 A kind of regulation and control SnS and SnS2pattern and the simple and easy method of structure conversion
CN112357951A (en) * 2020-10-16 2021-02-12 湖北大学 Solid-phase preparation method of SnS nanosheet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219192A (en) * 2011-05-17 2011-10-19 东华大学 Solar battery material SnS nanocrystal synthesized under conditions of high temperature and liquid phase by non-injection method
CN102730649A (en) * 2011-12-12 2012-10-17 北京理工大学 Method for preparing sulfide quantum dots on a basis of phase transfer technology
CN102897827A (en) * 2012-10-09 2013-01-30 东华大学 Method for phased synthesis of SnS, SnS2 or SnS/SnS2 heterojunction nanocrystalline material by one-step process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219192A (en) * 2011-05-17 2011-10-19 东华大学 Solar battery material SnS nanocrystal synthesized under conditions of high temperature and liquid phase by non-injection method
CN102730649A (en) * 2011-12-12 2012-10-17 北京理工大学 Method for preparing sulfide quantum dots on a basis of phase transfer technology
CN102897827A (en) * 2012-10-09 2013-01-30 东华大学 Method for phased synthesis of SnS, SnS2 or SnS/SnS2 heterojunction nanocrystalline material by one-step process

Non-Patent Citations (4)

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Title
BETTY YAN JIN LIANG等: "The influence of reaction temperatures and volume of oleic acid to synthesis", 《THIN SOLID FILMS》 *
HONGTAO LIU等: "Facile synthesis of monodisperse, size-tunable SnS nanoparticles potentially for solar cell energy conversion", 《NANOTECHNOLOGY》 *
KEIGO ASO等: "Synthesis of Needlelike and Platelike SnS Active Materials in High-Boiling Solvents and Their Application to All-Solid-State Lithium Secondary Batteries", 《CRYST. GROWTH DES.》 *
ZHENGTAO DENG等: "Colloidal synthesis of metastable zinc-blende IV–VI SnS nanocrystals with tunable sizes", 《NANOSCALE》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106115772A (en) * 2016-03-26 2016-11-16 上海大学 A kind of regulation and control SnS and SnS2pattern and the simple and easy method of structure conversion
CN112357951A (en) * 2020-10-16 2021-02-12 湖北大学 Solid-phase preparation method of SnS nanosheet
CN112357951B (en) * 2020-10-16 2022-04-19 湖北大学 Solid-phase preparation method of SnS nanosheet

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