CN102502793A - Preparation method of rod-shaped SnS nanocrystals - Google Patents

Abstract

The invention relates to a preparation method of rod-shaped SnS nanocrystals. The preparation method comprises the steps of: dissolving SnCl2 2H2O with ethylene glycol to obtain a solution A; adding a (NH4)2S solution to ethylene glycol to obtain a solution B; adding the solution A to the solution B, and stirring with a magnetic stirrer to form a precursor solution C; pouring the solution C to a hydrothermal reaction kettle, reacting under a temperature controlled mode, and naturally cooling to room temperature; and opening the hydrothermal reaction kettle, centrifuging and collecting the product, then respectively washing with deionized water and isopropanol, and then drying in a vacuum drying oven to obtain the final product rod-shaped SnS nanocrystals. According to the invention, SnS nanocrystals with uniform particle size are quickly prepared by adopting a microwave solvothermal method, the reaction is finished in the liquid phase at one time, post-treatment is not needed, the process equipment is simple and the reaction period is short.

Description

A kind of bar-shaped SnS preparation of nano crystal

Technical field

The present invention relates to a kind of preparation method of SnS nano-powder, be specifically related to the nanocrystalline method of the bar-shaped SnS of a kind of microwave solvent hot preparation.

Background technology

SnS is that IV～VI family has the semiconductor material of stratiform orthorhombic crystalline structure; Its spacer for

lattice parameter is: a=0.4329nm; B=1.1193nm, c=0.3984nm.SnS is the p type under normal conditions, and when Sn was imbued with, its conduction type will transfer the n type to by the p type.Its optics direct band gap and indirect band gap are respectively 1.3～1.5eV and 1.0～1.1eV; With the visible light in the solar radiation good Spectral matching is arranged; Photoelectric transformation efficiency reaches 25%; Be suitable as very much the light absorbing zone in the solar cell, also can be used as the near infrared detector and the photovoltage equipment of electroluminescent display.The Sn element and the S element earth content that constitute SnS in addition are abundant, and nontoxic, and therefore, SnS has received people in recent years gradually and greatly paid close attention to as a kind of novel photoelectric transition material with nontoxic, environmental protection of potential application foreground.

The method for preparing at present the SnS split has hydrothermal synthesis method [Rao.M.H, Jayalakshmi.M, Reddy.R.S.Chemistry Letters, 8 (2004) 1044-1045.]; TGA assisting alcohol-hydrothermal method [Zhu H L, Yang D R, Zhang H.Mater.Lett., 60 (2006); 2686-2689.], microwave assisting method [Chen D, Shen G, Tang K; Et al.J.Cryst.Growth, 260 (2004) 469-474.], ultrasonic liquid phase auxiliary law [Li H S, Lei TM; Feng Q, et al.J.Synth.Cryst., 34,200519-322.] etc.These methods or complex process, or apparatus expensive, or shortcoming such as poor repeatability, and product the reunion situation to occur serious, phenomenon such as pattern is inhomogeneous influences the photoelectric properties of SnS.

Summary of the invention

The object of the invention is to provide a kind of equipment simple; Easy handling; Preparation time is short; The nanocrystalline method of the bar-shaped SnS of employing microwave solvent hot preparation that cost is low can be prepared the rod-shaped powder that particle diameter of nanometer powder is 100～300nm by preparation method of the present invention, be uniformly dispersed and purity higher.

For achieving the above object, the technical scheme that the present invention adopts is:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.01mol/L～1.0mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.01mol/L～2.0mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C;

Sn wherein ²⁺: S ^2-Mol ratio be 1: 2～10: 1;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 40%～60%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 100 ℃～150 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind reaction 10min～120min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 40 ℃～70 ℃ again, gets the bar-shaped SnS nanocrystal of final product.

Described analytically pure (NH ₄) ₂The S of S solution ^2-Concentration>=8%.

The present invention adopts the hot method of microwave solvent, prepares even particle size SnS nanocrystal fast, once accomplishes owing to be reflected in the liquid phase, do not need post-processed, and processing unit is simple, and reaction time is short.

Description of drawings

Fig. 1 is prepared nanocrystalline X-ray diffraction (XRD) collection of illustrative plates of bar-shaped SnS of the embodiment of the invention 1;

Fig. 2 is the prepared nanocrystalline TEM photo of bar-shaped SnS of the embodiment of the invention 1.

Embodiment

Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.

Embodiment 1:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.05mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.1mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 1: 2;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 50%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 100 ℃, and pressure is 2.0MPa, naturally cools to room temperature behind the reaction 60min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 40 ℃, the bar-shaped SnS nanocrystal of final product.

The bar-shaped SnS nanocrystal of gained is analyzed with Japanese D/max2000PC x-ray diffractometer of science; The discovery product is rhombic form (Fig. 1); At 2 θ is 31.519 °; 31.880 °, 30.460 °, 27.440 ° of growth characteristics that have (111), (400), (011), (210) crystal face respectively.Sample with observing (Fig. 2) with the TEM-3010 of Jeol Ltd. (JEOL) type transmission electron microscope, can be found out that from photo prepared SnS nano crystal particles is approximately 200～500nm.

Embodiment 2:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.5mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.5mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 1: 1;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 60%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 120 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind the reaction 50min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 40 ℃, the bar-shaped SnS nanocrystal of final product.

Embodiment 3:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.2mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 1.2mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 1: 6;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 50%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 140 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind the reaction 40min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 40 ℃, the bar-shaped SnS nanocrystal of final product.

Embodiment 4:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.5mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 2.0mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 1: 4;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 40%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 150 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind the reaction 10min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 50 ℃, the bar-shaped SnS nanocrystal of final product.

Embodiment 5:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 1.0mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.01mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 10: 1

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 55%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 110 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind the reaction 120min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 70 ℃, the bar-shaped SnS nanocrystal of final product.

Embodiment 6:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.01mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.05mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C, wherein Sn ²⁺: S ^2-Mol ratio be 1: 5;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 45%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 130 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind the reaction 100min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 60 ℃, the bar-shaped SnS nanocrystal of final product.

Claims (2)

1. bar-shaped SnS preparation of nano crystal is characterized in that:

1) with analytically pure SnCl ₂2H ₂Sn is processed in the dissolving of O spent glycol ²⁺Concentration is the clear solution A of 0.01mol/L～1.0mol/L;

2) with analytically pure (NH ₄) ₂S solution spent glycol is mixed with S ^2-Concentration is the solution B of 0.01mol/L～2.0mol/L;

3) A solution is joined in the B solution with magnetic stirrer formation precursor solution C;

Sn wherein ²⁺: S ^2-Mol ratio be 1: 2～10: 1;

4) solution C is poured in the hydrothermal reaction kettle, compactedness is controlled at 40%～60%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, temperature is controlled at 100 ℃～150 ℃, and pressure naturally cools to room temperature less than 3.0MPa behind reaction 10min～120min;

5) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively 1～3 time then through centrifugal collection, places vacuum drying oven dry under 40 ℃～70 ℃ again, gets the bar-shaped SnS nanocrystal of final product.

2. bar-shaped SnS preparation of nano crystal according to claim 1 is characterized in that: described analytically pure (NH ₄) ₂The S of S solution ^2-Concentration>=8%.

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