CN102249199A - Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder - Google Patents

Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder Download PDF

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CN102249199A
CN102249199A CN2011101176411A CN201110117641A CN102249199A CN 102249199 A CN102249199 A CN 102249199A CN 2011101176411 A CN2011101176411 A CN 2011101176411A CN 201110117641 A CN201110117641 A CN 201110117641A CN 102249199 A CN102249199 A CN 102249199A
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powder
microwave
reaction
temperature
semiconductor material
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龙飞
邹正光
谢春艳
高洁
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Guilin University of Technology
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Guilin University of Technology
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Abstract

The invention discloses a microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder. The method comprises the following steps: adding metal salt and a sulfur source or selenium source into a beaker based on the mole ratio of an expected product, adding a solvent, evenly mixing and then transferring the obtained mixed solution to a microwave reaction kettle; after the reaction kettle is closed, heating the mixed solution to rated temperature in a microwave field, and performing heat preservation for rated time; and centrifugally washing the final product to obtain the target powder. In the method, the solvent is one or more of water, ethylenediamine, ethylene glycol, diamine and ethanol; the metal salt is the metal salt of Cu, In, Ga and Al; the sulfur source is thiourea or sulfur powder; and the selenium source is selenium powder or seleninic acid. The microwave-assisted solvothermal synthesis method has the beneficial effects that based on the heating and activation effect of the microwave field, reaction temperature is lowered and reaction time is shortened; and part of reaction that can not be made in the traditional high-pressure solvothermal synthesis process can be performed smoothly. The obtained semiconductor material nano-powder has the advantages of smaller grain size, pure phases, accurately controlled stoichiometric ratio of the phases and the like.

Description

The method of microwave-secondary solvent thermal synthesis I-III-VI family semiconductor material nano powder
Technical field
The present invention relates to the microwave-secondary solvent process for thermosynthesizing of a kind of I-III-VI family semiconductor material, institute's synthetic semiconductor material can be used to technical fields such as solar cell, photo-sensor, and especially being widely used in CIS/CIGS is the absorption layer of thin film solar cell material.
Background technology
Development of solar cell in recent years and exploitation obtain paying attention to day by day, and especially the exploitation of direct band gap material film solar cell becomes new research focus.Because it is few that thin film solar cell has a consumptive material, and the high characteristics of opto-electronic conversion greatly reduce the battery device cost.In the research of thin-film solar cells, Cu (In, Ga) Se 2, CuInS 2, CuInSe 2, Cu (In, Ga) (Se, S) 2, CuAlSe 2, Cu (In, Al) Se 2, Cu (In, Ga, Al) Se 2Has very high photoabsorption coefficient Deng semiconductor material, and Stability Analysis of Structures ([1] Karg F H.Development and Manufacturing of CIS, Thin Film Solar Modules.Solar Energy Materials and Solar Cells[J], 2001,66:645-653.[2] J.Olejn í cek, C.A.Kamler, A.Mirasano, et al.A non-vacuum process for preparing nanocrystalline CuIn 1-xGa xSe 2Materials involving an open-air solvothermal reaction, Solar Energy Materials﹠amp; Solar Cells[J] .2010 (94): 8-11.).Can be used for fields such as CIGS series thin film solar cell Development and Production and photo-sensor.Liquid phase is synthesized above-mentioned materials, and then film forming densification formation film is the absorption layer preparation technology that haves a great attraction.Yet the condition of conventional solvent thermal synthesis above-mentioned materials is comparatively harsh, the temperature of reaction height, and speed is also slower, and the required reaction times is longer.Generally, Cu (In, Ga) Se 2, CuInS 2, CuInSe 2, CuS, CuSe, Ga 2Se 3, Ga 2S 3, In 2Se 3, In 2S 3Solvent thermal synthetic need be in the high pressure enclosed environment under the comparatively high temps long-time insulation just can carry out ([3] Y.-G.Chun, K.-H.Kim, K.-H.Yoon.Synthesis of CuInGaSe 2Nanoparticles by solvothermal route.Thin Solid Films[J], 2005 (480481): 4649.[4] Yu-Hsiang A.Wang, Changqing Pan, Ningzhong Bao etal.Synthesis of ternary and quaternary CuIn xGa 1-xSe 2(0≤x≤1) semiconductor nanocrystals, Solid State Sciences[J] .2009 (11): 1961-1964.).Conventional solvent thermal synthesis mode exists equipment requirements higher, and temperature of reaction is higher, and length consuming time, product stoichiometric ratio are difficult to problems such as control ([6] SeJin Ahn, KiHyun Kim, KyungHoon Yoon.Nanoparticle derived Cu (In, Ga) Se 2Absorberlayer for thin film solar cells, Colloids and Surfaces A[J] .2008 (313-314): 171-174.).
Summary of the invention
The objective of the invention is with mantoquita, indium salt, gallium salt, aluminium salt and thiocarbamide, sulphur powder, selenium powder, selenous acid etc. is raw material, adopts the hot method of microwave-secondary solvent synthetic Cu (In, Ga) Se 2, CuInS 2, CuInSe 2, Cu (In, Ga) (Se, S) 2, CuAlSe 2, Cu (In, Al) Se 2, Cu (In, Ga, Al) Se 2Deng semiconductor material, and the matrix material that combines by above-mentioned materials.Microwave field has certain activation to reactant, and microwave heating simultaneously can guarantee that the temperature of reaction system field is even.
Concrete steps are:
In metal-salt and sulphur source or the mole proportioning adding beaker of selenium source by the expection product, add solvent then, pour into after mixing in the tetrafluoroethylene reactor.The airtight back of this reactor heat temperature raising in microwave field is incubated 10min-120min time rating after temperature rating 100-230 ℃; Reacting required reaction needs temperature and reaction times accurately to be controlled by the parameters setting of microwave generator; Obtain target powder after reaction back mixture process centrifuge washing, the vacuum-drying; The powder chemical constitution is by adding proportioning raw materials control, and the structure of powder is by proportioning raw materials, synthesis temperature and the common decision of reaction times control.
Described solvent is one or more in water, quadrol, ethylene glycol, diamine and the ethanol;
Described metal-salt is one or more in the metal-salt of Cu, In, Ga and Al;
Described sulphur source is thiocarbamide or sulphur powder;
Described selenium source is selenium powder or selenous acid.
The invention provides a kind of simple to operate, solvent thermal preparation technology that reaction activity power is strong, this technology has that synthesising reacting speed is fast, circulation ratio strong and reaction such as carries out thoroughly at characteristics.This technology greatly reduces temperature of reaction, has shortened the reaction times than conventional high-tension solvent thermal synthesis technique based on the heating and the activation of microwave field; The reaction that part can not be carried out in the conventional high-tension solvent thermal is synthetic is carried out smoothly.In addition, microwave-secondary solvent thermal synthesis prepared CuIn 1-xGa xSe 2Have advantages such as the product grain-size is less, thing is mutually pure, the stoichiometric ratio of thing phase can accurately be controlled Deng the semiconductor material nano powder.
Description of drawings
Fig. 1 is a synthesis process flow diagram of the present invention.
Fig. 2 is the embodiment of the invention 1 microwave solvent thermal synthesis CuIn 0.5Ga 0.5Se 2The SEM shape appearance figure of nano powder.
Fig. 3 is the synthetic CuIn of the embodiment of the invention 1 microwave solution heat 0.5Ga 0.5Se 2The XRD diffracting spectrum of nano powder.
Fig. 4 is the embodiment of the invention 3 microwave solvent thermal synthesis CuInS 2The SEM diffracting spectrum of nano powder.
Fig. 5 is the embodiment of the invention 3 microwave solvent thermal synthesis CuInS 2The XRD diffracting spectrum of nano powder.
Fig. 6 is the embodiment of the invention 4 microwave solvent thermal synthesis CuInSe 2The XRD diffracting spectrum of nano powder.
Fig. 7 is the embodiment of the invention 4 microwave solvent thermal synthesis CuInSe 2The SEM diffracting spectrum of nano powder.
Embodiment
Embodiment 1:(CuIn 0.5Ga 0.5Se 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, GaCl 3, the Se powder is a raw material, 1: 0.5: 0.5 in molar ratio: 2 take by weighing 0.17045g CuCl respectively 22H 2O, 0.146575g InCl 34H 2O, 0.08804g GaCl 3, 0.15792g Se powder adds in the microwave reaction kettle, adds quadrol 20ml; Put into the microwave instrument behind the capping still, set the microwave parameters: heating power 400W, the heating-up time is 15min, and temperature of reaction is 230 ℃, and the reaction times is 120min.After reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, promptly obtain CuIn 0.5Ga 0.5Se 2Nano powder.Sample is purified CuIn through the XRD analysis thing mutually 0.5Ga 0.5Se 2, through sem analysis, powder presents comparatively homogeneous granules shape of size distribution, the less about 100-200nm of particle size.
Embodiment 2:(CuIn 0.7Ga 0.3Se 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, GaCl 3, the Se powder is a raw material, 1: 0.3: 0.7 in molar ratio: 2 take by weighing 0.17045g CuCl respectively 22H 2O, 0.087945g InCl 34H 2O, 0.123256g GaCl 3, 0.15792g Se powder adds in the microwave reaction kettle, adds quadrol 20ml; Put into the microwave instrument behind the capping still, set the microwave parameters: heating power 400W, the heating-up time is 15min, and temperature of reaction is 230 ℃, and the reaction times is 60min.After reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, promptly obtain CuIn 0.7Ga 0.3Se 2Nano powder.Sample is purified CuIn through the XRD analysis thing mutually 0.3Ga 0.7Se 2, through sem analysis, powder presents comparatively homogeneous granules shape of size distribution, the less about 100200nm of particle size.
Embodiment 3:(CuInS 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, thiocarbamide (CH 4N 2S) be raw material, took by weighing 0.17045g CuCl in 1: 1: 2 in molar ratio 22H 2O, 0.29318g InCl 34H 2O, the 0.15224g thiocarbamide adds in the microwave reaction kettle, adds ethylene glycol 20ml; Put into the microwave instrument behind the capping still, set the microwave parameters: heating power 400W, the heating-up time is 10min, and temperature of reaction is 190 ℃, and the reaction times is 60min.After reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, promptly obtain CuInS 2Nano powder.Sample is CuInS through XRD analysis 2, through sem analysis, powder granule mainly is made up of spherical and sheet, the about 0.2 μ m-1 μ m of particle size size.
Embodiment 4:(CuInSe 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, selenous acid are raw material, take by weighing 0.17045gCuCl in 1: 1: 2 in molar ratio 22H 2O, 0.29318g InCl 34H 2O, the 0.25794g selenous acid adds in the microwave reaction kettle, adds 2ml hydrazine and 20ml ethylene glycol; Seal reactor and put into the microwave instrument, set microwave terms and conditions parameter: heating power 400W, the heating-up time is 10min, and temperature of reaction is 170 ℃, and the reaction times is 2h.After reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, obtain CuInSe 2Nano powder.Sample is CuInSe through XRD analysis 2, through sem analysis, there be the sheet structure coacervate of thickness about 0.1 μ m in the product, also there be the spherical particle of size about 1 μ m simultaneously.
Embodiment 5:(CuAlSe 2Synthesizing of powder)
With CuCl 22H 2O, AlCl 36H 2O, Se powder are raw material, take by weighing 0.17045gCuCl in 1: 1: 2 in molar ratio 22H 2O, 0.2413g AlCl 36H 2O, 0.15792g Se powder adds in the microwave reaction kettle, adds quadrol 20ml; Seal reactor and put into the microwave instrument, set the microwave parameters: heating power 400W, the heating-up time is 10min, and temperature of reaction is 200 ℃, and the reaction times is 60min.After reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, obtain CuAlSe 2Nano powder.
Embodiment 6:(CuIn 0.5Al 0.5Se 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, AlCl 36H 2O, Se powder are raw material, 1: 0.5: 0.5 in molar ratio: 2 take by weighing 0.17045g CuCl 22H 2O, 0.146575g InCl 34H 2O, 0.12067gAlCl 36H 2O, 0.15792g Se powder add in the microwave reaction kettle, add quadrol 20ml; Seal reactor and put into the microwave instrument, set microwave terms and conditions parameter: heating power 400W, the heating-up time is 15min, temperature of reaction is 220 ℃, reaction times is 120min, reaction naturally cools to below 100 ℃ after finishing, and reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several,, obtain CuIn with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing 0.5Al 0.5Se 2Nano powder.
Embodiment 7:(Cu (In, Ga, Al) Se 2Synthesizing of powder)
With CuCl 22H 2O, InCl 34H 2O, GaCl 3, AlCl 36H 2O, Se powder are raw material, 1: 0.5: 0.25 in molar ratio: take by weighing 0.17045g CuCl at 0.25: 2 22H 2O, 0.146575g InCl 34H 2O, 0.04402g GaCl 3, 0.12067g AlCl 36H 2O, the 0.15792g selenium powder adds in the microwave reaction kettle, adds quadrol 20ml; Seal reactor and put into the microwave instrument, set microwave terms and conditions parameter: heating power 400W, the heating-up time is 15min, temperature of reaction is 220 ℃, and the reaction times is 120min, after reaction finishes, naturally cool to below 100 ℃, reaction solution is transferred to the centrifuge tube from microwave reaction kettle, product is carried out centrifuge washing and separates, through distilled water and dehydrated alcohol centrifuge washing several, with the 80 ℃ of following vacuum-drying 8h in vacuum drying oven of the product behind the centrifuge washing, obtain Cu (In, Al, Ga) Se 2Nano powder.

Claims (1)

1. the preparation method of microwave-secondary solvent thermal synthesis 1-III-VI family semiconductor material nano powder is characterized in that concrete steps are:
In metal-salt and sulphur source or the mole proportioning adding beaker of selenium source by the expection product, add solvent then, pour into after mixing in the tetrafluoroethylene reactor; The airtight back of this reactor heat temperature raising in microwave field is incubated 10min-120min time rating after temperature rating 100-230 ℃; Reacting required reaction needs temperature and reaction times accurately to be controlled by the parameters setting of microwave generator; Obtain target powder after reaction back mixture process centrifuge washing, the vacuum-drying; The powder chemical constitution is by adding proportioning raw materials control, and the structure of powder is by synthesis temperature and the common decision of reaction times control;
Described solvent is one or more in water, quadrol, ethylene glycol, diamine and the ethanol;
Described metal-salt is the metal-salt of Cu, In, Ga and Al;
Described sulphur source is thiocarbamide or sulphur powder;
Described selenium source is selenium powder or selenous acid.
CN2011101176411A 2011-05-06 2011-05-06 Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder Pending CN102249199A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557117A (en) * 2012-03-08 2012-07-11 桂林理工大学 Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN102659084A (en) * 2012-05-14 2012-09-12 山东建筑大学 Preparation method of zinc selenide nanometer powder
CN103337555A (en) * 2013-06-09 2013-10-02 中南大学 Method for preparing copper indium selenium sulfur powder or thin film used in thin-film solar cell
CN103496737A (en) * 2013-09-26 2014-01-08 南京师范大学 Method for synthesizing copper-indium sulfide quantum dot in one step through microwave process
CN114988371A (en) * 2022-06-10 2022-09-02 南昌航空大学 Size-controllable solvent-thermal synthesized indium zinc selenide nanosheet and preparation method and application thereof

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CN101771099A (en) * 2008-12-30 2010-07-07 中国电子科技集团公司第十八研究所 Preparation method of copper-indium-gallium-selenium semiconductor film
CN101711970A (en) * 2009-12-18 2010-05-26 南京航空航天大学 Multifunctional ultrasonic microwave collaborative chemical reactor and method for preparing nano semiconductor chalcogenide by using same

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557117A (en) * 2012-03-08 2012-07-11 桂林理工大学 Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN102659084A (en) * 2012-05-14 2012-09-12 山东建筑大学 Preparation method of zinc selenide nanometer powder
CN103337555A (en) * 2013-06-09 2013-10-02 中南大学 Method for preparing copper indium selenium sulfur powder or thin film used in thin-film solar cell
CN103337555B (en) * 2013-06-09 2016-08-10 中南大学 A kind of copper and indium sulfur selenium powder body for thin-film solar cells or the preparation method of thin film
CN103496737A (en) * 2013-09-26 2014-01-08 南京师范大学 Method for synthesizing copper-indium sulfide quantum dot in one step through microwave process
CN114988371A (en) * 2022-06-10 2022-09-02 南昌航空大学 Size-controllable solvent-thermal synthesized indium zinc selenide nanosheet and preparation method and application thereof

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