CN103351022A - Method for preparing CuInS2 nanocrystals by using mother liquor through solvothermal process - Google Patents

Method for preparing CuInS2 nanocrystals by using mother liquor through solvothermal process Download PDF

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CN103351022A
CN103351022A CN2013102080434A CN201310208043A CN103351022A CN 103351022 A CN103351022 A CN 103351022A CN 2013102080434 A CN2013102080434 A CN 2013102080434A CN 201310208043 A CN201310208043 A CN 201310208043A CN 103351022 A CN103351022 A CN 103351022A
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nanocrystal
element source
solvent
mother liquid
liquid recycle
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高延敏
赵琴
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a method for preparing CuInS2 nanocrystals by using a mother liquor through a solvothermal process. The method comprises the following steps: 1, sequentially dissolving a Cu element source, an In element source and an S element source in a solvent, and stirring to obtain a clear solution; 2, transferring the clear solution to a pressure container for a reaction, and naturally cooling to room temperature after reaction ending; and 3, centrifuging products obtained in step 2, washing, and carrying out vacuum drying to obtain target products, wherein the solvent is one of or a mixture of N,N-dimethyl formamide and glycol. The method adopting the solvothermal process is cheap and convenient; the prepared nanocrystals have a uniform nanosheet structure, a high solid yield and a good optical absorption property; and the prepared CuInS2 nanocrystals have a highest optical absorption coefficient of 10<5> order of magnitude and a forbidden band width reaching 1.41eV, and the atom stoichiometric ratio of Cu:In:S is 1:0.89:1.93 and tends to a standard stoichiometric ratio of 1:1:2.

Description

A kind of mother liquid recycle solvent-thermal method prepares CuInS 2The method of nanocrystal
Technical field
The invention belongs to the photovoltaic material field, relate in particular to ternary semiconductor nano-powder CuInS 2The preparation method of nano crystal material.
Background technology
I-III-VI 2The N-type semiconductorN compound is the critical material of photovoltaic cell, especially CuInS 2Because having caused widely, its excellent combination property pays close attention to.Its advantage is: energy gap is 1.5eV, with the best energy gap of solar cell near (1.45eV); Uptake factor large (10 5), with its light absorbing zone as solar cell, thickness only needs 1～2 μ m, has reduced the consumption of raw material; Heat and electricity there is satisfactory stability; With CdTe, PbS, CuInSe 2Compare CuInS Deng other solar cell materials 2Do not contain any toxic ingredient, Environmental Safety.But present CuInS 2The laboratory photoelectric transformation efficiency of thin-film solar cells is about 13%, and is larger with theoretical yield (28%～32%) gap.
Prepare at present CuInS 2The method of material has a lot, as vulcanize method, chemical gas-phase method, electrodip process, spray pyrolysis method, continuous ionic layer absorption reaction method, radio frequency sputtering method, vacuum vapour deposition, solvent-thermal method etc. but these methods need to be carried out under high temperature (600 ℃～900 ℃) and high pressure mostly, or needing expensive large-scale instrument, cost of manufacture is high.The advantages such as wherein solvent-thermal method is simple because of preparation technology, reaction conditions is gentle, purity is high, pollution-free greatly reduce cost, are expected to realize industrialization production, become the most promising novel thin film solar cell material.At present, prepare the CuInS that purity is high, crystal formation is good by the single solvent system 2Still wayward; The solvent discharge amount is large in the preparation process, is unfavorable for low-carbon environment-friendly.
Summary of the invention
Goal of the invention: for the problem and shortage of above-mentioned existing existence, the purpose of this invention is to provide the sheet CuInS that a kind of mother liquid recycle solvent-thermal method preparation has chalcopyrite 2The method of nanocrystal, mother liquor can recycle among this preparation method, reduces the solution usage quantity, more environmental protection; The CuInS for preparing simultaneously 2The crystalline material photovoltaic performance is better.
Technical scheme: for achieving the above object, the present invention by the following technical solutions: a kind of mother liquid recycle solvent-thermal method prepares CuInS 2The method of nanocrystal may further comprise the steps:
A, Cu, In, S element source are dissolved in the mixed solvent successively, stir and obtain settled solution, and be 2～3 with sour regulation system pH; Wherein said mixing solutions is the mixed solution of DMF and ethylene glycol;
B, in reaction vessel, above-mentioned settled solution is at 170～200 ℃ of lower reaction 10～20h, reaction is cooled to room temperature after finishing;
C, product carried out centrifugation after, obtain solid product and wash, carry out at last vacuum-drying and obtain target product;
D, wherein carry out the recycle in mother liquor enters next round as mixed solvent the preparation process that obtains after the centrifugation among the above-mentioned steps c.
As preferably, described Cu element source is CuCl 22H 2O; The In element source is selected InCl 34H 2O; The S element source is selected CH 4N 2S.
As preferably, the mol ratio of described Cu, In, S element source is 1:1:2.3～2.8.
Further, described pressure container inner lining has tetrafluoroethylene.
Further, after product carries out centrifugation among the step c, successively by dehydrated alcohol and deionized water wash repeatedly.
As preferably, hydrochloric acid is adopted in the acid of transferring pH to use among the step a.
Beneficial effect: compared with prior art, the present invention has the following advantages: synthetic method adopts solvent-thermal method, and magnetron sputtering method, vacuum vapour deposition, sulfuration method, and it is a kind of cheapness, convenience, effective means that electrodip process etc. are compared; Apply mechanically by Recycling Mother Solution, reduced solvent load, reduced discharging of waste liquid and processing, effectively reduce production cost; By adopting binary mixed solvent to replace traditional single organic solvent, prepared sample is a kind of even sheet structure, solid-phase to yield high (average yield is about 93.5%), absorbing properties is better, energy gap is suitable nano photovoltaic material; Adopt solvent-thermal method to synthesize a class direct band-gap semicondictor material.Such material photoabsorption coefficient is up to 10 5The order of magnitude, energy gap reaches 1.42eV, near the desirable energy gap 1.45eV of solar cell; The CuInS of the present invention's preparation 2Nanocrystal, Cu, In, three kinds of element atom meterings of S are than comparing 1:1:2 for all being tending towards the standard chemical metering.
Description of drawings
Fig. 1 is the CuInS that the present invention prepares 2The X-ray diffraction of nanocrystal (XRD) collection of illustrative plates;
Fig. 2 is the CuInS that the present invention prepares 2The scanning electron microscope of nanocrystal (SEM) picture;
Fig. 3 is the CuInS that the present invention prepares 2The energy spectrogram (EDS) of nanocrystal;
Fig. 4 is the CuInS that the present invention prepares 2The energy gap figure of nanocrystal.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment only is used for explanation the present invention and is not used in and limits the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Embodiment 1
1) takes by weighing 0.4651g CuCl with analytical balance 22H 2O, 0.8000g InCl 34H 2O, 0.5192gCH 4N 2S places 40mlN successively, in the dinethylformamide (DMF), stirs and makes it abundant dissolving, gets yellow settled solution.N (CuCl wherein 22H 2O) ︰ n (InCl 34H 2O) ︰ n (CH 4N 2S)=1 ︰ 1 ︰ 2.5.
2) measure 40ml ethylene glycol (EG) and slowly pour solution in the described step 1) into, stir and make it Uniform Dispersion, get colorless cleared solution.Add concentrated hydrochloric acid regulation system pH=2-3.
3) with described step 2) in mixing solutions change in the polytetrafluoroethyllining lining autoclave pressure that volume is 100mL after sealing, behind reaction 12h under 190 ℃ of conditions, naturally cool to room temperature.
4) with reaction feed liquid centrifugal 15min in electric centrifuge of described step 3), then rotating speed 3000r/min pours out the upper strata stillness of night, stand-by.Sample is used respectively dehydrated alcohol and deionized water wash for several times.Products therefrom is 60 ℃ of dry 6h in vacuum drying oven, take out sample, obtain the black solid powder, weigh encapsulation.
Embodiment 2
1) takes by weighing 0.4651g CuCl with analytical balance 22H 2O, 0.8000g InCl 34H 2O, 0.5192gCH 4N 2S places the at first mother liquor of solid-liquid separation of embodiment 1 successively, stirs to make it Uniform Dispersion.
2) in the mixing solutions of described step 1), add concentrated hydrochloric acid regulation system pH=2-3.
3) with described step 2) in mixing solutions change in the polytetrafluoroethyllining lining autoclave pressure that volume is 100mL after sealing, behind reaction 12h under 190 ℃ of conditions, naturally cool to room temperature.
4) with reaction feed liquid centrifugal 15min in electric centrifuge of described step 3), then rotating speed 3000r/min pours out the upper strata stillness of night, stand-by.Sample is used respectively dehydrated alcohol and deionized water wash for several times.Products therefrom is 60 ℃ of dry 6h in vacuum drying oven, take out sample, obtain the black solid powder, weigh encapsulation.
Embodiment 3
1) takes by weighing 0.4651g CuCl with analytical balance 22H 2O, 0.8000g InCl 34H 2O, 0.5192gCH 4N 2S places the at first mother liquor of solid-liquid separation of embodiment 2 successively, stirs to make it Uniform Dispersion.
2) in the mixing solutions of described step 1), add concentrated hydrochloric acid regulation system pH=2-3.
3) with described step 2) in mixing solutions change in the polytetrafluoroethyllining lining autoclave pressure that volume is 100mL after sealing, behind reaction 12h under 190 ℃ of conditions, naturally cool to room temperature.
4) with reaction feed liquid centrifugal 15min in electric centrifuge of described step 3), then rotating speed 3000r/min pours out the upper strata stillness of night, stand-by.Sample is used respectively dehydrated alcohol and deionized water wash for several times.Products therefrom is 60 ℃ of dry 6h in vacuum drying oven, take out sample, obtain the black solid powder, weigh encapsulation.
Embodiment 4
1) takes by weighing 0.4651g CuCl with analytical balance 22H 2O, 0.8000g InCl 34H 2O, 0.5192gCH 4N 2S places the at first mother liquor of solid-liquid separation of embodiment 3 successively, stirs to make it Uniform Dispersion.
2) in the mixing solutions of described step 1), add concentrated hydrochloric acid regulation system pH=2-3.
3) with described step 2) in mixing solutions change in the polytetrafluoroethyllining lining autoclave pressure that volume is 100mL after sealing, behind reaction 12h under 190 ℃ of conditions, naturally cool to room temperature.
4) with reaction feed liquid centrifugal 15min in electric centrifuge of described step 3), then rotating speed 3000r/min pours out the upper strata stillness of night, stand-by.Sample is used respectively dehydrated alcohol and deionized water wash for several times.Products therefrom is 60 ℃ of dry 6h in vacuum drying oven, take out sample, obtain the black solid powder, weigh encapsulation.
Embodiment 5
1) takes by weighing 0.4651g CuCl with analytical balance 22H 2O, 0.8000g InCl 34H 2O, 0.5192gCH 4N 2S places the at first mother liquor of solid-liquid separation of embodiment 4 successively, stirs to make it Uniform Dispersion.
2) in the mixing solutions of described step 1), add concentrated hydrochloric acid regulation system pH=2-3.
3) with described step 2) in mixing solutions change in the polytetrafluoroethyllining lining autoclave pressure that volume is 100mL after sealing, behind reaction 12h under 190 ℃ of conditions, naturally cool to room temperature.
4) with reaction feed liquid centrifugal 15min in electric centrifuge of described step 3), then rotating speed 3000r/min pours out the upper strata stillness of night, stand-by.Sample is used respectively dehydrated alcohol and deionized water wash for several times.Products therefrom is 60 ℃ of dry 6h in vacuum drying oven, take out sample, obtain the black solid powder, weigh encapsulation.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Fig. 1 is the XRD figure of front 4 times of mother liquid recycle (being example 1, example 2, example 3 and example 4) preparations products therefrom, 4 batch samples all in (112), (200), chalcopyrite CuInS appearred in (220), (312), (400), (316) crystal face 2The characteristic diffraction peak of nanocrystal is without obvious Impurity Absorption peak.The research discovery, along with the increase of mother liquid recycle number of times, sample characteristic absorption peak half-peak width reduces.
Fig. 2 is the CuInS of front 4 times of mother liquid recycle (being example 1, example 2, example 3 and example 4) preparation 2The SEM figure of crystal, as seen from the figure, the sample of preparation forms the approximately flower-shaped microballoon of 2 μ m with the even sheet for the first time, along with the increase of mother liquid recycle number of times, prepared CuInS 2The nanocrystal microsphere diameter reduces gradually.Because during mother liquid recycle, contain last residual sample or reaction source in the solvent each time, can affect the growth of crystal.
The mother liquor that Fig. 3 collects for first centrifugation after applying mechanically at every turn, as can be seen from Fig.: the mother liquor color is deepened gradually, and it is more shallow that rear mother liquid obtained color is applied mechanically in first three time.
Fig. 4 is the CuInS of front 4 times of mother liquid recycle (being example 1, example 2, example 3 and example 4) preparation 2The EDS power spectrum of nanocrystal, only contain Cu, In, three kinds of elements of S in the sample, and Cu, In, three kinds of element atom meterings of S all are tending towards the standard chemical metering than 1 ︰, 1 ︰ 2 than being respectively 1:0.89:1.91,1:0.89:1.91,1:0.93:1.94,1:1.00:1.97.
Fig. 4 is the CuInS of (example 4) preparation behind the mother liquid recycle four times 2The uv-absorbing energy gap figure of nanocrystal, the energy gap that can learn crystal from figure is 1.42eV, approaches with theoretical value 1.5eV, and satisfies the desirable energy gap 1.45eV of solar cell.

Claims (6)

1. a mother liquid recycle solvent-thermal method prepares CuInS 2The method of nanocrystal may further comprise the steps:
A, Cu, In, S element source are dissolved in the mixed solvent successively, stir and obtain settled solution, and be 2～3 with sour regulation system pH; Wherein said mixing solutions is the mixed solution of DMF and ethylene glycol;
B, in reaction vessel, above-mentioned settled solution is at 170～200 ℃ of lower reaction 10～20h, reaction is cooled to room temperature after finishing;
C, product carried out centrifugation after, obtain solid product and wash, carry out at last vacuum-drying and obtain target product;
D, wherein carry out the recycle in mother liquor enters next round as mixed solvent the preparation process that obtains after the centrifugation among the above-mentioned steps c.
2. described mother liquid recycle solvent-thermal method prepares CuInS according to claim 1 2The method of nanocrystal is characterized in that: described Cu element source is CuCl 22H 2O; The In element source is selected InCl 34H 2O; The S element source is selected CH 4N 2S.
3. described mother liquid recycle solvent-thermal method prepares CuInS according to claim 2 2The method of nanocrystal is characterized in that: the mol ratio of described Cu, In, S element source is 1:1:2.3～2.8.
4. described mother liquid recycle solvent-thermal method prepares CuInS according to claim 3 2The method of nanocrystal is characterized in that: described pressure container inner lining has tetrafluoroethylene.
5. described mother liquid recycle solvent-thermal method prepares CuInS according to claim 4 2The method of nanocrystal is characterized in that: after product carries out centrifugation among the step c, successively by dehydrated alcohol and deionized water wash repeatedly.
6. described mother liquid recycle solvent-thermal method prepares CuInS according to claim 5 2The method of nanocrystal is characterized in that: hydrochloric acid is adopted in the acid of transferring pH to use among the step a.
CN2013102080434A 2013-05-28 2013-05-28 Method for preparing CuInS2 nanocrystals by using mother liquor through solvothermal process Pending CN103351022A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107059131A (en) * 2017-04-21 2017-08-18 南京信息工程大学 A kind of semiconductor nano and preparation method and application
CN115490260A (en) * 2022-10-20 2022-12-20 延安大学 CuInS rich in S vacancies 2 Preparation method and application of ultrathin nanosheet
CN115571912A (en) * 2022-10-09 2023-01-06 重庆文理学院 Preparation method of sulfide phase nano material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵琴等: ""反应介质对溶剂热法合成CuInS2纳米晶体的影响"", 《武汉理工大学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107059131A (en) * 2017-04-21 2017-08-18 南京信息工程大学 A kind of semiconductor nano and preparation method and application
CN115571912A (en) * 2022-10-09 2023-01-06 重庆文理学院 Preparation method of sulfide phase nano material
CN115490260A (en) * 2022-10-20 2022-12-20 延安大学 CuInS rich in S vacancies 2 Preparation method and application of ultrathin nanosheet

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Application publication date: 20131016