CN102557117A - Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves - Google Patents
Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves Download PDFInfo
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- CN102557117A CN102557117A CN2012100624612A CN201210062461A CN102557117A CN 102557117 A CN102557117 A CN 102557117A CN 2012100624612 A CN2012100624612 A CN 2012100624612A CN 201210062461 A CN201210062461 A CN 201210062461A CN 102557117 A CN102557117 A CN 102557117A
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Abstract
The invention discloses a method for thermally synthesizing a Cu2ZnSnS4 (CZTS) semiconductor material by a solvent through microwaves. The method comprises the following steps of: adding copper salt, zinc salt, tin salt and a sulphur source into a beaker according to a preset molar ratio, adding the solvent, mixing uniformly and pouring the mixture into a reaction kettle, and placing the reaction kettle into a microwave field for heating after being closed, keeping the rated temperature for rated time after the temperature is raised to the rated temperature, and performing centrifugation, washing and vacuum drying on an obtained product to obtain the Cu2ZnSnS4 semiconductor material. The solvent can be one or more of water, glycol, ethanediamine and diamine, and the sulphur source can be sulfourea or sulphur powder. In the method, the Cu2ZnSnS4 semiconductor material prepared by the microwave-assisted solvent thermal synthesis process has high purity, and has the advantages of high synthesis speed, simple reaction device, low cost and easiness in process control.
Description
Technical field:
The present invention relates to a kind of Cu
2ZnSnS
4(CZTS) the microwave solvent thermal synthesis technology of semiconductor material, institute's synthetic semiconductor material can be used to solar cell, photo-sensor field.
Background technology:
Cu
2ZnSnS
4Semiconductor material can be used for CZTS series thin film solar cell and relative photo power conversion device Development and Production.Cu commonly used at present
2ZnSnS
4The compound method of semiconductor material has vacuum thermal evaporation method, electron-beam vapor deposition method, sputtering method, spray pyrolysis, electrodip process, sol-gel method and molecular beam epitaxy etc.; The required reaction conditions of in them some is comparatively harsh; To having relatively high expectations of equipment, reaction cost is high, the miscellaneous difficult control of technology; Other speed of response are slow, and need under HTHP, carry out the reaction of long period could obtain.
Summary of the invention
The objective of the invention is with mantoquita, zinc salt, pink salt and sulphur source is raw material, under microwave-assisted, utilizes the synthetic fast Cu of solvent-thermal method
2ZnSnS
4Semiconductor material.
Concrete steps are:
A mole proportioning (1～3) is pressed in mantoquita, zinc salt, pink salt and sulphur source: (0.5～1.5): (0.5～1.5): mix (4～6); Add solvent; Solvent load is above-mentioned raw materials to be dissolved fully and solvent volume is no more than 2/3 of reactor volume; Pour reaction kettle after mixing into, putting into microwave field after airtight heats, and treats to be incubated 0.5～12 hour after temperature rises to 100～250 ℃; Products therefrom process zero(ppm) water and absolute ethyl alcohol centrifuge washing 2～3 times, the vacuum drying oven inner drying under 70～90 ℃ got Cu in 7～9 hours then
2ZnSnS
4Semiconductor material;
Said solvent is one or more in water, terepthaloyl moietie, quadrol and the diamine;
Said mantoquita is one or more in venus crystals, cupric chloride and the cupric nitrate;
Said zinc salt is one or more in zinc acetate, zinc chloride and the zinc nitrate;
Said pink salt is tin tetrachloride or tindichloride;
Said sulphur source is thiocarbamide or sulphur powder.
The present invention has advantages such as resultant velocity is fast, product is pure, cost is low, technology controlling and process is easy.In addition, microwave-assisted solvent thermal synthesis technology is compared with common high pressure solvent thermal synthesis technique, and reaction unit is simpler, speed of response is faster, the reaction process controllability is better, title product purity is higher.
Description of drawings
Fig. 1 is a synthesis process flow diagram of the present invention.
Fig. 2 is embodiment of the invention microwave solvent thermal synthesis Cu
2ZnSnS
4The SEM shape appearance figure of semiconductor material.
Fig. 3 is embodiment of the invention microwave solvent thermal synthesis Cu
2ZnSnS
4The XRD diffracting spectrum of semiconductor material.
Embodiment
Embodiment:
2.995 gram venus crystalss, 1.642 gram zinc acetates, 2.628 gram tin tetrachloride and thiocarbamide 2.283 grams are poured in the beaker, put into one and stir magneton, add the dissolving of 30ml terepthaloyl moietie again; Be transferred to magnetic stirring apparatus, treat to pour the microwave reaction kettle that volume is 50ml into after raw material stirring evenly, install reaction unit; Design temperature is 250 ℃; Be incubated 3 hours, insulation naturally cools to room temperature after finishing, and reaction solution is transferred in the beaker; Then respectively through zero(ppm) water and absolute ethyl alcohol centrifuge washing 3 times, with the 80 ℃ of following vacuum-drying 8 hours in vacuum drying oven of the product behind the centrifuge washing.Product is Cu through XRD analysis
2ZnSnS
4, through the electronic scanning electronic microscope photos, product mainly is made up of irregular particulate state powder, and the about 1-2 μ of the size of particulate state powder m can find out through the picture that amplifies, and the particulate state powder is reunited by many little irregular flaps and is formed.
Claims (1)
1. microwave solvent thermal synthesis Cu
2ZnSnS
4The method of semiconductor material is characterized in that concrete steps are:
A mole proportioning (1～3) is pressed in mantoquita, zinc salt, pink salt and sulphur source: (0.5～1.5): (0.5～1.5): mix (4～6); Add solvent; Solvent load is above-mentioned raw materials to be dissolved fully and solvent volume is no more than 2/3 of reactor volume; Pour reaction kettle after mixing into, putting into microwave field after airtight heats, and treats to be incubated 0.5～12 hour after temperature rises to 100～250 ℃; Products therefrom process zero(ppm) water and absolute ethyl alcohol centrifuge washing 2～3 times, the vacuum drying oven inner drying under 70～90 ℃ got Cu in 7～9 hours then
2ZnSnS
4Semiconductor material;
Said solvent is one or more in water, terepthaloyl moietie, quadrol and the diamine;
Said mantoquita is one or more in venus crystals, cupric chloride and the cupric nitrate;
Said zinc salt is one or more in zinc acetate, zinc chloride and the zinc nitrate;
Said pink salt is tin tetrachloride or tindichloride;
Said sulphur source is thiocarbamide or sulphur powder.
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| CN2012100624612A CN102557117A (en) | 2012-03-08 | 2012-03-08 | Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves |
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| CN2012100624612A CN102557117A (en) | 2012-03-08 | 2012-03-08 | Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011261A (en) * | 2012-12-02 | 2013-04-03 | 桂林理工大学 | Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves |
| CN103043628A (en) * | 2012-12-02 | 2013-04-17 | 桂林理工大学 | Method for thermally synthesizing sphalerite structure CZTSSe semiconductor material through solvent under synergistic action of ultrasonic microwave |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles |
| CN103474512A (en) * | 2013-09-26 | 2013-12-25 | 南京师范大学 | Method for compounding sulfide copper zinc tin quantum dots in one-step mode through microwave method |
| CN103794373A (en) * | 2013-12-26 | 2014-05-14 | 中国矿业大学 | Cu2ZnSnS4 / MWCNT nano composite counter electrode for dye-sensitized solar cell and preparation method thereof |
| CN104370302A (en) * | 2014-10-23 | 2015-02-25 | 上海交通大学 | Nano-pouring synthetic method of copper-zinc-tin-sulfur nano-crystal |
| US20150135994A1 (en) * | 2012-10-04 | 2015-05-21 | International Business Machines Corporation | Solution processing of kesterite semiconductors |
| CN105197985A (en) * | 2015-09-17 | 2015-12-30 | 上海大学 | Preparation method for synthesizing super-long wurtzite structure Cu2ZnSnS4 nanorod in one step through solvothermal method |
| CN108558202A (en) * | 2018-07-27 | 2018-09-21 | 望江县天长光学科技有限公司 | A kind of optical glass of high refractive index |
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| CN102060273A (en) * | 2010-11-05 | 2011-05-18 | 桂林理工大学 | Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system |
| CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
| CN102249199A (en) * | 2011-05-06 | 2011-11-23 | 桂林理工大学 | Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder |
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2012
- 2012-03-08 CN CN2012100624612A patent/CN102557117A/en active Pending
Patent Citations (3)
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| CN102060273A (en) * | 2010-11-05 | 2011-05-18 | 桂林理工大学 | Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system |
| CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
| CN102249199A (en) * | 2011-05-06 | 2011-11-23 | 桂林理工大学 | Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder |
Non-Patent Citations (1)
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| 蔡倩等: "溶剂热法制备球状Cu2ZnSnS4纳米晶及其表征", 《物理化学学报》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150135994A1 (en) * | 2012-10-04 | 2015-05-21 | International Business Machines Corporation | Solution processing of kesterite semiconductors |
| CN103011261A (en) * | 2012-12-02 | 2013-04-03 | 桂林理工大学 | Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves |
| CN103043628A (en) * | 2012-12-02 | 2013-04-17 | 桂林理工大学 | Method for thermally synthesizing sphalerite structure CZTSSe semiconductor material through solvent under synergistic action of ultrasonic microwave |
| CN103011261B (en) * | 2012-12-02 | 2014-08-20 | 桂林理工大学 | Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves |
| CN103043628B (en) * | 2012-12-02 | 2014-10-29 | 桂林理工大学 | Method for thermally synthesizing sphalerite structure CZTSSe semiconductor material through solvent under synergistic action of ultrasonic microwave |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles |
| CN103474512A (en) * | 2013-09-26 | 2013-12-25 | 南京师范大学 | Method for compounding sulfide copper zinc tin quantum dots in one-step mode through microwave method |
| CN103474512B (en) * | 2013-09-26 | 2016-01-27 | 南京师范大学 | The method of microwave method one-step synthesis sulfide copper zinc tin quantum dot |
| CN103794373A (en) * | 2013-12-26 | 2014-05-14 | 中国矿业大学 | Cu2ZnSnS4 / MWCNT nano composite counter electrode for dye-sensitized solar cell and preparation method thereof |
| CN104370302A (en) * | 2014-10-23 | 2015-02-25 | 上海交通大学 | Nano-pouring synthetic method of copper-zinc-tin-sulfur nano-crystal |
| CN105197985A (en) * | 2015-09-17 | 2015-12-30 | 上海大学 | Preparation method for synthesizing super-long wurtzite structure Cu2ZnSnS4 nanorod in one step through solvothermal method |
| CN108558202A (en) * | 2018-07-27 | 2018-09-21 | 望江县天长光学科技有限公司 | A kind of optical glass of high refractive index |
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Application publication date: 20120711 |