CN102718249B - Method for preparing CuInS2 nanocrystalline and CuInS2/ZnS core-shell structure nanocrystalline - Google Patents
Method for preparing CuInS2 nanocrystalline and CuInS2/ZnS core-shell structure nanocrystalline Download PDFInfo
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- CN102718249B CN102718249B CN201210138338.4A CN201210138338A CN102718249B CN 102718249 B CN102718249 B CN 102718249B CN 201210138338 A CN201210138338 A CN 201210138338A CN 102718249 B CN102718249 B CN 102718249B
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Abstract
The invention discloses a method for preparing CuInS2 nanocrystalline and CuInS2/ZnS core-shell structure nanocrystalline, which is characterized in that stearic acid indium is reacted with cuprous iodide with the same mole in a mixed solution containing oleic acid, superfluous dodecanethiol and octadecene to obtain the CuInS2 nanocrystalline, a zinc stearate solution is added to obtain the CuInS2/ZnS core-shell structure nanocrystalline. The CuInS2 nanocrystalline and the CuInS2/ZnS core-shell structure nanocrystalline have the characteristics of homogeneous phase, low toxicity, good monodispersity, strong repeatability, wide spectrum coverage and high fluorescent quantum yield, wherein the fluorescent quantum yield of the CuInS2 nanocrystalline can reach as high as 8.7%; and the fluorescent quantum yield of the CuInS2/ZnS nanocrystalline can reach as high as 60%. The method of the invention has the advantages of easy available and stable raw materials, safe and convenient operation and no requirement of rigorous condition; thereby the laboratory large-scale preparation and industrial production of the CuInS2 nanocrystalline and CuInS2/ZnS core-shell structure nanocrystalline realize the possibility.
Description
Technical field
The invention belongs to field of inorganic nano material, be specifically related to CuInS
2the preparation method of nanocrystalline (quantum dot).The invention still further relates to CuInS
2the preparation method of/ZnS core shell structural nano brilliant (quantum dot)
Background technology
Quantum dot (quantum dots, QDs) is three-dimensional limited, approximate spherical inorganic semiconductor nanocrystal.Due to the optical property of the nanocrystalline excellence of inorganic semiconductor, aspect fluorescent mark, attracted numerous scientists' research interest.For example, living organisms Imaging-PAM has become current most active subject direction.Regrettably,, a little less than the fluorescence nano penetrativity of VISIBLE LIGHT EMISSION, limited its application aspect living organisms fluorescence imaging.In order to overcome the problem a little less than penetration power, a series of near-infrared quantum dots (750-900nm) are developed, and mainly comprise II-VI (CdTe/CdSe, CdSe/ZnTe), IV-VI (PbS, PbSe), II-V (Cd
3p
2), but because these quantum dots include Cd and the poisonous element of Pb, easily cause environmental pollution.So, the CuInS of low toxicity
2near-infrared quantum dots gradually becomes the focus of research.
CuInS
2direct band gap, the semiconductor nano that bandwidth is 1.45eV.The people such as Peng are metal precursor with stearic acid indium and neutralized verdigris, adopt the hot injection method of organic phase, have synthesized high quality, near infrared CuInS
2nanocrystalline, but synthetic method is complicated, poor repeatability, synthetic nanocrystalline fluorescence quantum yield low (lower than 3%); The people such as Zhong have synthesized CuInS with cuprous acetate and indium acetate
2nanocrystalline, but its emission peak maximum is at 740nm, does not reach near infrared region; Afterwards, the method for the people such as Li based on the same with Zhong, was metal precursor with cuprous iodide and indium acetate, had synthesized near infrared CuInS
2nanocrystalline, but owing to there is no the reactive behavior of two metal precursors of balance, it is nanocrystalline is homogeneous phase not, and system contains CuS and In
2s
3impurity, cannot be separated.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of CuInS
2nanocrystalline preparation method, the method is easy and simple to handle, and raw material is easy to get, and reaction conditions is gentle, synthetic CuInS
2nanocrystalline homogeneous phase, low toxicity, and monodispersity is good, and repeatability is strong, and fluorescence quantum yield is relatively high.
Another technical problem to be solved by this invention is to provide a kind of CuInS
2/ ZnS core shell structural nano is brilliant, the relative CuInS of fluorescence quantum yield
2nanocrystalline had a further raising.
For solving above-mentioned first technical problem, technical scheme provided by the invention comprises the steps:
1) by amount of substance than putting into there-necked flask for the indium acetate of 1:12 and stearic acid, under nitrogen atmosphere, in 140
o c reaction 5 hours, is cooled to room temperature, then through washing with acetone, filtration, vacuum-drying, obtains stearic acid indium crude product;
2) stearic acid of the amount of substance of itself and 8 times of indium acetates in step 1) is put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) by waiting cuprous iodide and the stearic acid indium powder of amount of substance to add in the mixed solvent containing the oleic acid of 200-500 μ l, the Dodecyl Mercaptan of 0.7-1.25ml and vaccenic acid, under nitrogen atmosphere, be warming up to 70
oc, keeps 30-60min, is then warming up to 200-250
oc, reacts no more than 5 hours, is cooled to room temperature; Be dispersed in chloroform and methyl alcohol mixed liquor, then add acetone precipitation, centrifugation, discards supernatant liquid, and throw out is taken out to vacuum-drying, obtains CuInS
2nanocrystalline.If preparation CuInS
2/ ZnS,, in this step, does not need to be cooled to room temperature and carries out centrifugal purification process, and directly carrying out next step reaction.
Vaccenic acid is as the reaction solvent of body series, and for the not significant impact of product performance, its consumption does not have strict restriction yet, is preferably 10ml.
4) dropwise drip the Zinic stearas that is dissolved in tri octyl phosphine and vaccenic acid, keep 30 minutes, be then cooled to room temperature, be dispersed in chloroform and methyl alcohol mixed liquor, added acetone precipitation, centrifugation, discard supernatant liquid, throw out is taken out to vacuum-drying, obtain CuInS
2/ ZnS is nanocrystalline;
In the amount of substance of described Zinic stearas and step 3), the amount of substance of cuprous iodide is than being 2-10:1.
The present invention prepares pulverous stearic acid indium by two-step approach, and using the mixed solvent (Dodecyl Mercaptan is simultaneously as the sulphur source of reacting) that ten Er Liu Chun ﹑ oleic acid and vaccenic acid react with cuprous iodide as stearic acid indium, preferably balance the activity of stearic acid indium and cuprous iodide, prepare homogeneous phase, low toxicity, monodispersity is good, wave spectrum coverage is wide CuInS
2nanocrystalline, the scope of its fluorescent emission peak position is 695-835nm, and fluorescence quantum yield is up to 8.7%; Through Passivation Treatment, synthetic CuInS
2the quantum yield of/ZnS core shell structural nano crystalline substance is greatly improved, and the scope of fluorescent emission peak position is 620-820nm, and fluorescence quantum yield is up to 60%.Adopt the present invention, raw material is easy to get stable, and simple and safe operation does not need exacting terms, makes the extensive preparation in laboratory and even suitability for industrialized production become possibility.The methods such as the quantum dot uv-visible absorption spectra obtaining, fluorescence spectrum, high-resolution-ration transmission electric-lens, x-ray powder crystalline diffraction characterize.
Accompanying drawing explanation:
Fig. 1 is stearic acid indium (In (SA) prepared by the present invention
3) infared spectrum;
Fig. 2 is the prepared CuInS of the present invention
2nanocrystalline energy spectrogram;
Fig. 3 is the prepared 3-4nm CuInS that is of a size of of the present invention
2nanocrystalline HRTEM picture;
Fig. 4 is the CuInS of different-grain diameter
2nanocrystalline fluorescence (a) and uv-visible absorption spectroscopy (b);
Fig. 5 is the CuInS of different emission peaks
2nanocrystalline quantum yield (a) and fluorescence lifetime collection of illustrative plates (b);
Fig. 6 is the prepared CuInS of the present invention
2and CuInS
2the X-ray powder diffraction figure that/ZnS is nanocrystalline;
Fig. 7 is with 3-4 nm CuInS
2the CuInS that nanocrystalline (a) makes for core
2the HRTEM picture that/ZnS (b) is nanocrystalline.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further detailed explanation.
Implementation process of the present invention comprises following four steps:
1) by amount of substance than putting into there-necked flask for the indium acetate of 1:12 and stearic acid, under nitrogen atmosphere, in 140
o c reaction 5 hours, is cooled to room temperature, then through washing with acetone, filtration, vacuum-drying, obtains stearic acid indium crude product;
2) by itself and 8 times to step 1) in the stearic acid of amount of substance of indium acetate put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) by waiting cuprous iodide and the stearic acid indium powder of amount of substance to add in the mixed solvent containing the oleic acid of 200-500 μ l, the Dodecyl Mercaptan of 0.7-1.25ml and vaccenic acid, under nitrogen atmosphere, be warming up to 70
oc, keeps 30-60min, is then warming up to 200-250
oc, reacts no more than 5 hours, is cooled to room temperature; Be dispersed in chloroform and methyl alcohol mixed liquor, then add acetone precipitation, centrifugation, discards supernatant liquid, and throw out is taken out to vacuum-drying, obtains CuInS
2nanocrystalline.If preparation CuInS
2/ ZnS,, in this step, does not need to be cooled to room temperature and carries out centrifugal purification process, and directly carrying out next step reaction.
Vaccenic acid is as the reaction solvent of body series, and for the not significant impact of product performance, its consumption does not have strict restriction yet, is preferably 10ml.
4) dropwise drip the Zinic stearas that is dissolved in tri octyl phosphine and vaccenic acid, keep 30 minutes, be then cooled to room temperature, be dispersed in chloroform and methyl alcohol mixed liquor, added acetone precipitation, centrifugation, discard supernatant liquid, throw out is taken out to vacuum-drying, obtain CuInS
2/ ZnS is nanocrystalline;
In the amount of substance of described Zinic stearas and step 3), the amount of substance of cuprous iodide is than being 2-10:1.
Embodiment 1
1) take the In (Ac) of 2.92g
3put into there-necked flask with 95% the stearic acid of 36g, under nitrogen atmosphere, in 140
o c reaction 5 hours, is cooled to room temperature, then uses washing with acetone three times, after filtration, after vacuum-drying, obtain stearic acid indium crude product;
2) 95% the stearic acid of itself and 24g is put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) the stearic acid indium powder of the CuI of 0.0191g and 0.1g is dissolved in the mixed solvent of the oleic acid, the Dodecyl Mercaptan of 1 ml and the vaccenic acid of 10ml that contain 210 μ l, under nitrogen atmosphere, is warming up to 70
oc, keeps 45 minutes, is then warming up to 225
oc, reacts 55 minutes (and in reaction, to 5,10,20,30,40,50 minutes, sampling respectively), is cooled to room temperature, be dispersed in the chloroform and methyl alcohol mixed liquor of 5ml, then added the acetone of 30ml, centrifugation, throw out is taken out, and vacuum-drying, can obtain CuInS
2nanocrystalline.
As can be seen from Figure 1, stearic acid (SA) is at 1715cm
-1it is very weak that the charateristic avsorption band at place becomes on the spectrogram of stearic acid indium, and this spectrum peak is-in COOH group-C=O-vibration peak, illustrate that stearic acid has been converted into stearic acid indium, and the 1540cm occurring from stearic acid indium (In (SA) 3) spectrogram
-1the absorption peak at place, COO-vibration peak can further be proven.From can finding out synthetic product containing Cu, In, tri-kinds of elements of S by spectrogram of Fig. 2.The CuInS that the embodiment of the present invention obtains as can be seen from Figure 3
2the nanocrystalline 3-4nm that is of a size of.The CuInS obtaining when the step 3) reaction times is respectively 5,10,20,30,40,50,55 minutes in embodiment 1
2nanocrystalline fluorescence and uv-visible absorption spectroscopy are shown in Fig. 4, as can be seen from Figure 4, and synthetic CuInS
2the scope of nanocrystalline fluorescent emission peak position is 695-835nm, and its fluorescence quantum yield is up to 8.7% as can be seen from Figure 5.
1) take 2.92gIn (Ac)
3put into there-necked flask with 95% the stearic acid of 36g, under nitrogen atmosphere, in 140
o c reaction 5 hours, is cooled to room temperature, then uses washing with acetone three times, filters and obtains stearic acid indium, after vacuum-drying, obtains stearic acid indium crude product;
2) 95% the stearic acid of itself and 24g is put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) 95% the stearic acid indium of the CuI of 0.0191g and 0.1g is dissolved in and contains 210 oleic acid of μ l, in the mixed solvent of the vaccenic acid of the Dodecyl Mercaptan of 1ml and 10ml, under nitrogen atmosphere, be warming up to 70
oc, keeps 45 minutes, is then warming up to 225
oc, reacts 30 minutes;
4) 0.316g Zinic stearas is dissolved in the mixed solvent of trioctylphosphine phosphorus of 2ml vaccenic acid and 0.5ml, with syringe, in 10-20 minute, dropwise splash into, keep 30 minutes, then be cooled to room temperature, be dispersed in the chloroform and methyl alcohol mixed liquor of 5 ml, then add the acetone of 30ml, centrifugation, throw out is taken out, and vacuum-drying, can obtain CuInS
2nanocrystalline, its quantum yield has reached 60%.
Fig. 6 is respectively gained CuInS
2nanocrystalline and CuInS
2the X-ray powder diffraction figure that/ZnS is nanocrystalline, with the data consistent of the people such as Peng report (R.G. Xie, M. Rutherford, X.G. Peng, J. Am. Chem. Soc. 131 (2009) 5691).Fig. 7 is respectively synthetic CuInS
2nanocrystalline (a) and with this big or small CuInS
2nanocrystalline for the CuInS of nucleosynthesis
2/ ZnS(b) the high-resolution electron microscopy figure of core-shell type nano crystalline substance finds from Fig. 7, and the nanocrystalline particle diameter after involucrum becomes large, illustrates that core-shell type nano crystalline substance has successfully been synthesized.
In the situation that other conditions are constant, contriver, by changing temperature of reaction and the reaction times of the step 3) of embodiment 1 and embodiment 2, finds that working as temperature of reaction is 200
oc, the reaction times while reaching the highest fluorescent emission peak position (835nm) is 5 hours, and temperature of reaction is 250
oc, the reaction times while reaching minimum fluorescent emission peak position (695nm) is 2 minutes.
In the situation that other conditions are constant, contriver passes through to change the amount of Zinic stearas in embodiment 2, when the add-on of discovery Zinic stearas is 0.126g, and the CuInS of preparation
2the nanocrystalline quantum yield of/ZnS is 32%, when the add-on of Zinic stearas is 0.632g, and the CuInS of preparation
2the nanocrystalline quantum yield of/ZnS is 45%, and add-on is 0.316 o'clock, the CuInS of preparation
2the nanocrystalline quantum yield of/ZnS reaches 60%.
Claims (2)
1. a CuInS
2nanocrystalline preparation method, is characterized in that: comprise the following steps:
1) by amount of substance than putting into there-necked flask for the indium acetate of 1:12 and stearic acid, under nitrogen atmosphere, in 140
oc reaction 5 hours, is cooled to room temperature, then through washing with acetone, filtration, vacuum-drying, obtains stearic acid indium crude product;
2) by itself and 8 times to step 1) in the stearic acid of amount of substance of indium acetate put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) by waiting cuprous iodide and the stearic acid indium powder of amount of substance to add in the mixed solvent containing the oleic acid of 200-500 μ L, the Dodecyl Mercaptan of 0.7-1.25mL and vaccenic acid, under nitrogen atmosphere, be warming up to 70
oc, keeps 30-60min, is then warming up to 200-250
oc, reacts no more than 5 hours, is cooled to room temperature; Be dispersed in chloroform and methyl alcohol mixed liquor, then add acetone precipitation, centrifugation, discards supernatant liquid, and throw out is taken out to vacuum-drying, obtains CuInS
2nanocrystalline.
2. a CuInS
2the preparation method of/ZnS core shell structural nano crystalline substance, is characterized in that: comprise the following steps:
1) by amount of substance than putting into there-necked flask for the indium acetate of 1:12 and stearic acid, under nitrogen atmosphere, in 140
oc reaction 5 hours, is cooled to room temperature, then through washing with acetone, filtration, vacuum-drying, obtains stearic acid indium crude product;
2) by itself and 8 times to step 1) in the stearic acid of amount of substance of indium acetate put into there-necked flask, the same step 1) of other reaction conditions, reaction product, after washing with acetone, filtration, vacuum-drying, grinds to form stearic acid indium powder;
3) by waiting cuprous iodide and the stearic acid indium powder of amount of substance to add in the mixed solvent containing the oleic acid of 200-500 μ L, the Dodecyl Mercaptan of 0.7-1.25mL and vaccenic acid, under nitrogen atmosphere, be warming up to 70
oc, keeps 30-60min, is then warming up to 200-250
oc, reacted after 0-55 minute, dropwise dripped the Zinic stearas that is dissolved in tri octyl phosphine and vaccenic acid, kept 30 minutes, then be cooled to room temperature, be dispersed in chloroform and methyl alcohol mixed liquor, add acetone precipitation, centrifugation, discard supernatant liquid, throw out is taken out to vacuum-drying, obtain CuInS
2/ ZnS is nanocrystalline;
The amount of substance of described Zinic stearas is 2-10:1 with the amount of substance of cuprous iodide ratio.
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| CN102951676B (en) * | 2012-11-22 | 2014-07-16 | 温州大学 | One-step synthetic preparation method of CuInS2 nanowires |
| CN103215034A (en) * | 2013-03-15 | 2013-07-24 | 河南大学 | Preparation method of high-quality CuInZnxS2+x/ZnS (0 <=x<=1) semiconductor nanocrystalline with core-shell structure |
| CN104894635B (en) * | 2015-04-27 | 2018-03-16 | 武汉理工大学 | Controllable copper antimony sulphur nanocrystalline material of size and preparation method thereof |
| CN104861964B (en) * | 2015-05-14 | 2016-06-29 | 中国科学院广州能源研究所 | A kind of CuInS2/In2S3/ ZnS two-layer core shell structured fluorescence quantum dot and preparation method thereof |
| US20210040385A1 (en) * | 2018-02-15 | 2021-02-11 | Osaka University | Core-shell semiconductor nanoparticles, production method thereof, and light-emitting device |
| CN108328647B (en) * | 2018-02-28 | 2020-04-10 | 武汉理工大学 | Wurtzite structure CuInS2Method for preparing nanocrystalline |
| CN115340863B (en) * | 2022-06-29 | 2023-11-14 | 河北大学 | Near infrared core-shell structure quantum dot CuInS 2 Method for synthesizing ZnS |
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