CN101559978A - Solvent thermal synthesis method of Wurtzite structure CuInS* - Google Patents

Abstract

The invention discloses a solvent thermal synthesis method of Wurtzite structure CuInS2. The method comprises the following steps of: weighing 1-2mmol CuCl2.2H2O, 1-2mmol InCl3.4H2O and 3-6mmol thiourea, putting the substances in a beaker and adding the substances in neovaricaine solvent; pouring the obtained uniform dark blue solution to a reaction kettle, putting the reaction kettle in an oven with the temperature of 170-210 DEG C for reacting 12-24h, and subsequently naturally cooling to room temperature; and finally washing the collected and cooled product with distilled water and absolute ethyl alcohol sequentially to obtain black solid samples. The method has the advantages of simple operation, low cost, simple product cleaning and no pollution to the environment and the like, and synthesizes Wurtzite structure CuInS2 metastable phase with one step through the simple one-step solvent thermal synthesis method, thus being beneficial to broaden the application range of I-III-VI2 group ternary chalcogenide semiconductor. The Wurtzite structure CuInS2 metastable new phase can be applied in the aspects of opto-electrical devices, non-linear opto-electrical devices, opto-electrical solar cell materials, laser diodes and the like.

Description

A kind of wurtzite-type structure C uInS 2Solvent process for thermosynthesizing

Technical field

The present invention relates to a kind of inorganic synthetic method, specifically is a kind of wurtzite-type structure C uInS ₂Solvent process for thermosynthesizing.

Background technology

I-III-VI ₂The ternary chalcongen compound semiconductor ABM of family ₂(A=Cu, Ag; B=Al, Ga, In; M=S, Se Te) at normal temperatures and pressures, has yellow copper structure (tetragonal) usually.Because of being with a wide range of applications at aspects such as photoelectric device, device for non-linear optical, photovoltaic solar cells material, laser diodes, it receives much concern.But under harsh experiment condition such as the situation of high temperature and high pressure, also can obtain unordered zink sulphide (cubic structure) or wurtzite structure (hexagonal structure).For example Binsma etc. in 1980 at research Cu ₂S-In ₂S ₃Find during the mixture phasor: the yellow copper structure CuInS that reaction generates about 850 ℃ ₂Stable below 980 ℃ the time, when temperature is elevated to more than 980 ℃ and more than 1045 ℃ the time, the transformation to unordered zink sulphide (cubic structure) or wurtzite structure (hexagonal structure) has taken place respectively.High temperature X-ray diffraction analysis has confirmed zink sulphide phase CuInS ₂Existence.But high temperature phase CuInS ₂Can not stable existence, when temperature reduces, be transformed into cryogenic yellow copper structure again.From the angle of crystalline structure, most of I-III-VI ₂Family's ternary chalcongen compound can be realized under given conditions from order to unordered conversion, thereby obtain the not product of jljl phase.Recently, Pan etc. is at nano materials CuInS ₂The time, (oleyl amine, Dodecyl Mercaptan) synthesized wurtzite structure CuInS first in high boiling solvent ₂, but this synthetic method complexity, the starting material costliness will be used organic reagents such as hexane, chloroform in the product cleaning process, and environment has been caused certain pollution.

Summary of the invention

The invention provides a kind of wurtzite-type structure C uInS ₂Solvent process for thermosynthesizing, it is simple to operate, cost is low, product cleaning is simple, can not pollute environment.

Technical scheme of the present invention is:

A kind of wurtzite-type structure C uInS ₂Solvent process for thermosynthesizing, it is characterized in that: comprise by following reaction ratio and carry out following steps:

(1), takes by weighing 1-2mmol CuCl ₂2H ₂O, 1-2mmol InCl ₃4H ₂O and 3-6mmol thiocarbamide are put into beaker, add in the thanomin solvent, ultra-sonic dispersion 10-15 minute, obtain uniform navy blue solution;

(2), above-mentioned uniform navy blue solution is poured in the autoclave, the autoclave of sealing is placed in 170-210 ℃ the baking oven reaction 12-24 hour, naturally cools to room temperature subsequently;

(3), will collect cooled product at last, use distilled water, absolute ethanol washing successively, vacuum-drying obtains the solid of black.

Described a kind of wurtzite-type structure C uInS ₂Solvent process for thermosynthesizing, it is characterized in that: may further comprise the steps:

(1), the ratio that takes by weighing amount of substance is 1: the CuCl of 0.8-1.2: 2.8-3.2 ₂2H ₂O, InCl ₃4H ₂O and thiocarbamide are put into beaker, add thanomin and carry out ultra-sonic dispersion 10-15 minute as solvent, obtain uniform navy blue solution;

(2), then above-mentioned uniform navy blue solution is poured in the autoclave, the autoclave of sealing is placed in 170-210 ℃ the baking oven reaction 12-24 hour, naturally cools to room temperature subsequently;

(3), will collect cooled product at last, use distilled water, absolute ethanol washing successively,, obtain the solid of black at 50-70 ℃ of following vacuum-drying 3-5 hour.

The thanomin consumption is 2-100ml.

The present invention has simple to operate, and cost is low, and product cleaning is simple, can be, and the present invention is by a simple step solvent thermal synthesis method to advantages such as environment pollute, one-step synthesis wurtzite structure CuInS ₂Metastable phase helps widening I-III-VI ₂The range of application of family's ternary chalcongen compound semiconductor.Wurtzite structure CuInS ₂Metastable cenotype can be applicable to photoelectric device, device for non-linear optical, photovoltaic solar cells material, aspects such as laser diode.

Description of drawings

Fig. 1 is synthetic CuInS of the present invention ₂The XRD diffraction pattern figure of sample.

Fig. 2 is synthetic CuInS of the present invention ₂The x-ray fluorescence spectrometry figure of sample.

Fig. 3 is synthetic CuInS of the present invention ₂The X-ray diffraction pattern figure of sample.

Fig. 4 is the CuInS of jljl phase not ₂Ultraviolet-visible-near-infrared spectrum figure.

Fig. 5 is synthetic CuInS of the present invention ₂The photoluminescence spectra figure of sample.

Embodiment

Synthetic method of the present invention is as follows:

(1), takes by weighing 1-2mmol CuCl ₂2H ₂O, 1-2mmol InCl ₃4H ₂O and 3-6mmol thiocarbamide are put into beaker, add the 40ml thanomin, ultra-sonic dispersion 10-15 minute, obtain uniform navy blue solution;

(2), above-mentioned uniform navy blue solution is poured in the autoclave, reactor is placed in 170-210 ℃ the baking oven reaction 12-24 hour, naturally cools to room temperature subsequently;

(3), then collect cooled product, use distilled water, absolute ethanol washing successively,, obtain black solid samples 60 ℃ of following vacuum-dryings 4 hours;

(4) material is identified:

(a), through the X-ray diffractometer analysis revealed: the product of preparation is wurtzite structure CuInS ₂Metastable cenotype, and diffraction pattern carried out a series of numerical fitting;

(b), the x-ray fluorescence spectrometry of sample shows: the constituent content ratio of product is 1: 1: 2;

(c), the annealing performance of sample shows: wurtzite structure CuInS ₂In room temperature and be stable below 250 ℃, surpass 400 ℃ and begin to have taken place phase transformation, surpass 550 ℃ phase transformation has taken place fully;

(b), the CuInS of jljl phase not ₂Ultraviolet-visible-near-infrared spectrum show: the CuInS of jljl phase not ₂, to the absorbing state difference of light.

Claims (3)

1, a kind of wurtzite-type structure C uInS ₂Solvent process for thermosynthesizing, it is characterized in that: comprise by following reaction ratio and carry out following steps:

(1), takes by weighing 1-2mmol CuCl ₂2H ₂O, 1-2mmol InCl ₃4H ₂O and 3-6mmol thiocarbamide are put into beaker, add in the thanomin solvent, ultra-sonic dispersion 10-15 minute, obtain uniform navy blue solution;

(2), above-mentioned uniform navy blue solution is poured in the autoclave, the autoclave of sealing is placed in 170-210 ℃ the baking oven reaction 12-24 hour, naturally cools to room temperature subsequently;

(3), will collect cooled product at last, use distilled water, absolute ethanol washing successively, vacuum-drying obtains the solid of black.

2, a kind of wurtzite-type structure C uInS according to claim 1 ₂Solvent process for thermosynthesizing, it is characterized in that: may further comprise the steps:

(1), the ratio that takes by weighing amount of substance is 1: the CuCl of 0.8-1.2: 2.8-3.2 ₂2H ₂O, InCl ₃4H ₂O and thiocarbamide are put into beaker, add thanomin and carry out ultra-sonic dispersion 10-15 minute as solvent, obtain uniform navy blue solution;

(2), then above-mentioned uniform navy blue solution is poured in the autoclave, the autoclave of sealing is placed in 170-210 ℃ the baking oven reaction 12-24 hour, naturally cools to room temperature subsequently;

(3), will collect cooled product at last, use distilled water, absolute ethanol washing successively,, obtain the solid of black at 50-70 ℃ of following vacuum-drying 3-5 hour.

3, a kind of wurtzite-type structure C uInS according to claim 1 ₂Solvent process for thermosynthesizing, it is characterized in that: the thanomin consumption is 20-100ml.

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