CN102583557B - Preparation method for tower-pyramid gamma-MnS microcrystal - Google Patents

Abstract

A preparation method for tower-pyramid gamma-MnS microcrystal comprises the following steps that: manganous nitrate is added into deionized water to obtain solution A; thioacetamide is added into the solution A and is subjected to ultrasonic dispersion to obtain solution B; citric acid is added into the solution B to form a precursor, namely solution C; the solution C is poured into a flask to be sealed; the sealed flask is put into a reaction kettle with microwaves, ultraviolet and ultrasonic waves to be heated and irradiated by a ultraviolet lamp to obtain solution D; the solution D is put into a microwave hydrothermal reaction kettle, and then the reaction kettle is sealed, is put into a temperature-pressure double-control microwave hydrothermal reaction instrument and is naturally cooled to be at a room temperature after reaction is finished; and products are collected in a centrifugal way and then are dried in a draught drying cabinet to obtain a final product, namely the tower-pyramid gamma-MnS microcrystal. According to the invention, as the simple microwave hydrothermal method with the auxiliary ultraviolet is adopted, a reaction period is short, energy consumption is low, and the reaction is finished in a liquid phase with two steps and does not need post-processing. The prepared tower-pyramid gamma-MnS microcrystal is regularly tower-pyramid-shaped and is relatively uniform in size.

Description

The preparation method of a kind of tower taper γ-MnS crystallite

Technical field

The invention belongs to the preparation method of semiconductor material with wide forbidden band manganese sulfide, be specifically related to the preparation method of a kind of tower taper γ-MnS crystallite.

Background technology

Transient metal sulfide is important broad-band gap inorganic semiconductor compound-material, has become the international focus of shortwave photoelectric semiconductor material research rapidly because of its important physics-chem characteristic.MnS is the weak magnetic semiconductor material of VIIB-VIA family, and 3 kinds of phases are arranged, i.e. octahedral coordination, green and stable rock salt structure α-MnS (RS); Tetrahedral coordination, pink colour, zincblende lattce structure β-MnS and wurtzite structure γ-MnS that Jie is steady.The three has anti-ferromagnetism, and Neel temperature is respectively 152K (RS) and 90K (ZB/W), at room temperature only is characteristics such as 3.7eV just like its band-gap energy also, and it is had a wide range of applications in short wavelength's photoelectricity apparatus field.As: sun power is selected coating, solar cell, photo-sensor, photo-conductor etc.Metastable β and γ-MnS are at 100-400 ℃ of α-MnS that easily changes stable state into, and this transformation is irreversible.Metastable MnS compares with the MnS of stable state, has shown more special chemical property, electric property, optical property and magnetic performance.

At present, synthetic field at manganese sulfide, special microtexture and size tool a lot of interesting character, as special electricity, optics, magnetic performance, so caused domestic and international material supply section scholar's extensive interest and pay close attention to for their research synthetic and performance.In this field, pattern has very big influence for the physical properties of material.Be one for the control of material pattern and size for the material supply section scholar and be rich in challenging front line science.Ge etc. utilize Manganous chloride tetrahydrate and sulphur powder, and (chemical vapor deposition, CVD) method has made the MnS monocrystal nanowire in 850 ℃ of reaction 120min by chemical Vapor deposition process.[GE?J?P，LI?Y?D.Controllable?CVD?route?to?CoS?and?MnS?single-crystal?nanowires[J].Chem?Commun，2003，19：2498-2499.]。In addition, adopt hydrothermal method [ZHANG Y C, WANG H, WANG B, et al.Low-temperature hydro-thermal synthesis of pure metastable γ-manganese sulfide (MnS) crys-tallites[J] .J Cryst Growth, 2002,243 (1): 214-217.], solvent-thermal method [ZHANG X H, CHEN Y Q, JIA C, et al.Two-step solvothermal synthe-sis of α-MnS spheres:Growth mechanism and characterization[J] .Mater Lett, 2008,62:125-127.], molecular beam epitaxy (molecular beam epitaxy, MBE) [OKAJIMA M, TOHDA J.Heteroepitaxial growth of MnS on GaAs substrates[J] .J Cryst Growth, 1992,117 (1-4): 810-815.], circumfluence method [Qi Yuanchun, Zhao Yanbao, Xu Hongtao. the preparation that the controlled γ-MnS of pattern is nanocrystalline and sign [J]. chemical research, 2006,17 (6): 60-62.] also the success the manganese sulfide crystal that has synthesized different-shape, but current synthetic method is often because using conventional sulphur source (thiocarbamide, sodium sulphite, Sulfothiorine etc.) produce a large amount of poisonous unpleasant hydrogen sulfide, the technological operation complexity is difficult to control.Therefore, be necessary to develop some simple, economic, effective, eco-friendly methods and prepare the manganese sulfide nanometer semiconductor structure.

Summary of the invention

The objective of the invention is to propose the preparation method of a kind of tower taper γ-MnS crystallite.This preparation method combines ultraviolet and microwave, and precursor liquid is through the irradiation of UV-light, and activation energy reduces, shortened microwave hydrothermal reaction time, reduced temperature of reaction, be a kind of environmental friendliness, with low cost, simple to operate, good reproducibility, the method for suitable scale operation.

For achieving the above object, the technical solution used in the present invention is:

1) with analytically pure Mn (NO ₃) ₂4H ₂O joins in the deionized water, makes Mn ²⁺Concentration is the clear solution A of 0.1mol/L-1.5mol/L;

2) add analytically pure thioacetamide in the solution A, make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 1-8 gets solution B with the solution ultra-sonic dispersion;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 0.1mol/L-2.0mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 50-80 ℃, magnetic agitation speed is 300-500r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 50-150min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 35%-65%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 120-280 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.2-1.8Mpa, reaction times 30min-120min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 50-80 ℃ of drying in electric drying oven with forced convection.

The present invention adopts simple ultraviolet to assist microwave-hydrothermal method preparation technology, after precursor liquid adopts the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave to carry out uv irradiating, reduced the activation energy of system in the microwave reaction process, and reaction time is short, energy consumption is low, be reflected in the liquid phase and finish in two steps, do not need post-processed.The γ that makes-MnS crystallite has the tower taper of rule, and size is homogeneous comparatively.

Description of drawings

Fig. 1 is the X-ray diffractometer analysis chart of tower taper γ-MnS crystallite of preparing of the present invention;

Fig. 2 is the electron scanning micrograph of tower taper γ-MnS crystallite of preparing of the present invention.

Embodiment

Below in conjunction with drawings and Examples the present invention is described in further detail.

Embodiment 1:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 0.12mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 1.2, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 0.2mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 75 ℃, magnetic agitation speed is 450r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 60min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 60%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 130 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.5Mpa, reaction times 110min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 55 ℃ of dryings in electric drying oven with forced convection.

Embodiment 2:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 0.1mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 2, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 0.4mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 50 ℃, magnetic agitation speed is 400r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 70min;

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 50%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 140 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.8Mpa, reaction times 90min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 60 ℃ of dryings in electric drying oven with forced convection.

Embodiment 3:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 0.4mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 1, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 0.1mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 68 ℃, magnetic agitation speed is 380r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 50min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 55%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 150 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 1.0Mpa, reaction times is 80min, and reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 65 ℃ of dryings in electric drying oven with forced convection.

Embodiment 4:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 0.8mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 4, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 1mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 65 ℃, magnetic agitation speed is 350r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 100min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 60%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 160 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 1.3Mpa, reaction times 70min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 70 ℃ of dryings in electric drying oven with forced convection.

Embodiment 5:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 1.0mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 5, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 1.2mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 65 ℃, magnetic agitation speed is 300r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 120min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 65%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 280 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 1.8Mpa, reaction times 30min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 80 ℃ of dryings in electric drying oven with forced convection.

Embodiment 6:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 1.2mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 6, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 1.6mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 62 ℃, magnetic agitation speed is 320r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 130min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 62%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 230 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 1.5Mpa, reaction times 50min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 75 ℃ of dryings in electric drying oven with forced convection.

Embodiment 7:

1) with analytically pure manganous nitrate (Mn (NO ₃) ₂4H ₂O) join in the deionized water, make Mn ²⁺Concentration is the clear solution A of 1.5mol/L;

2) in solution A, add analytically pure thioacetamide (C ₂H ₅NS), make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1: 8, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 2.0mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 80 ℃, magnetic agitation speed is 500r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 150min

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 35%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 120 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.2Mpa, reaction times 120min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 50 ℃ of dryings in electric drying oven with forced convection.

The MnS crystal of gained with Japanese D/max2000PCX-x ray diffractometer x analytic sample of science, is found that product is that the γ-MnS structure (JCPDS 40-1289) of six side's phases is seen Fig. 1.This sample is observed with the JSM-6390A type scanning electronic microscope that Japanese firm produces, and as can be seen from Figure 2 obtained metastable phase pencil shape γ-MnS is long is 2-4 μ m, and size is homogeneous comparatively.

Claims (1)

1. the preparation method of tower taper γ-MnS crystallite is characterized in that:

1) with analytically pure Mn (NO ₃) ₂4H ₂O joins in the deionized water, makes Mn ²⁺Concentration is the clear solution A of 0.1mol/L-1.5mol/L;

2) add analytically pure thioacetamide in the solution A, make Mn in the solution ²⁺/ C ₂H ₅The mol ratio of NS is 1:1-8, and the solution ultra-sonic dispersion is got solution B;

3) solution adds analytically pure citric acid in the B, makes that the concentration of citric acid is 0.1mol/L-2.0mol/L in the solution, forms precursor solution C;

4) precursor solution C is poured in the flask seal, then the flask of sealing is put into the synthetic extractive reaction instrument of the three-in-one body of microwave ultraviolet excess sound wave, select " temperature-time " operating mode for use, temperature is arranged on 50-80 ℃, magnetic agitation speed is 300-500r/min, add the ultraviolet energy, the output rating of ultraviolet lamp is 300W, gets solution D behind the reaction 50-150min;

5) solution D is put into microwave hydrothermal reaction kettle, compactedness is 35%-65%, sealed reactor then, put it in the two control of the temperature and pressure microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature control of described temperature control mode is at 120-280 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.2-1.8MPa, reaction times 30min-120min, reaction naturally cools to room temperature after finishing;

6) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing 3-5 time respectively then through centrifugal collection, obtains final product tower taper γ-MnS crystallite 50-80 ℃ of drying in electric drying oven with forced convection.

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