CN1174080C - Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot - Google Patents
Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot Download PDFInfo
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- CN1174080C CN1174080C CNB021391521A CN02139152A CN1174080C CN 1174080 C CN1174080 C CN 1174080C CN B021391521 A CNB021391521 A CN B021391521A CN 02139152 A CN02139152 A CN 02139152A CN 1174080 C CN1174080 C CN 1174080C
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Abstract
The present invention discloses a preparation method of II-VI core/shell mold quantum dots of CdSe/CdS, CdSe/ZnS, etc. In the method, inorganic compounds of cadmium chloride or zinc acetate, etc. are used as a raw material; the CdTe/CdS of the core/shell mold and CdSe/ZnS quantum dot are prepared under a moderate condition; in the method, metal organic compounds of the grade of Zn(CH3)2, Cd(CH3)2 in the literature, which are inflammable, explosive and expensive, are avoided. The method has advantages of safe operation, convenience and good repeatability. The obtained products have good monodispersity, great improved photoluminescent property and high stability; the quantum yield can be increased to 60-80% from 20-30% of that of a quantum dot before being coated. The method can be widely used as a fluorescent marked object used for biological detection and analysis.
Description
Technical field
The present invention relates to the preparation method of core/shell type quantum dots such as a kind of CdSe/CdS, CdSe/ZnS.
Background technology
Quantum dot be radius less than or approach the semiconductor nano crystal grain of exciton Bohr radius, because of having distinctive quantum size effect and surface effects, it is had broad application prospects at aspects such as luminescent material, photosensors.CdSe, II-VI type quantum dots such as CdS, has special and good visible region fluorescent emission character, its fluorescence intensity is strong, bleaching speed is slow, fluorescence spectrum is narrow, highly sensitive, and excitation spectrum continuous distribution, the fluorescence spectra position can be regulated and control by the size that changes quantum dot, many II-VI type quantum dots, as CdS, CdSe, the emmission spectrum of CdTe etc. is crossed over the visible range, can be at the different quantum dot of a certain wavelength simultaneous excitation, obtain the different visible emissivity spectrum of wide region, carry out multiplex fluorescence and detect.These characteristics make quantum dot can be used as the novel fluorescent marker of a class, have broad application prospects in biomolecules identification and in detecting.
Need pure, stable, monodispersed high quality nanocrystal in the practical application, and this to be common settling process can not get, so the preparation of relevant quantum dot becomes hot research in recent years.CdO such as Peng, Cd (Ac)
2, CdCO
3Salt of weak acid and selenium powder Deng cadmium are made raw material, use TOPO, and HDA, stearic acid etc. have synthesized the II-VI type quantum dot of excellent property as solvent.Though can successfully synthesize II-VI type quantum dots such as CdSe in this way, because the usually easy oxidation of quantum dot, the instability of preparation, and there are a large amount of defectives on the surface, has a strong impact on its quantum yield.Take to coat the semiconductor material that another kind of crystalline structure is similar, band gap is bigger on single quantum dot surface, make the core/shell type nanocrystal, then can strengthen its stability, and surperficial radiationless recombinable site is passivated, excite defective to improve its photoluminescent property greatly thereby reduce.Peng, Cd (CH such as Bowen-Katari
3)
2, Zn (CH
3)
2Make raw material Deng organometallic compound, the CdSe/CdS or the CdSe/ZnS quantum dot that make core/shell structure at the CdS or the ZnS of CdSe surface coverage suitable thickness, can prevent that not only CdSe is oxidized, strengthen the stability of nuclear greatly, and product has good monodispersity, and quantum yield has also been brought up to 30-50% from original 5-15%.Yet, because Cd (CH
3)
2, Zn (CH
3)
2Deng metallorganics severe toxicity, instability, explosive, therefore, it is extremely dangerous to make raw material with these compounds, the appointed condition harshness that needs.
Summary of the invention
The present invention is exactly the preparation method that a kind of CdSe/CdS or CdSe/ZnS core/shell type quantum dot are provided at the problems referred to above, and this method does not need harsh appointed condition, simple and safe operation, and materials safety is easy to get, and is cheap.
Technical scheme provided by the invention is: the preparation method of a kind of CdSe/CdS or CdSe/ZnS core/shell type quantum dot, adopt following step:
(a) selenium powder is dissolved in tri-n-octyl phosphine and the dioctylamine, makes the storing solution of selenium, will vulcanize two (trimethyl silyl) [(TMS)
2S] be dissolved in tri-n-octyl phosphine and the dioctylamine, make the storing solution of sulfide;
(b) Cadmium oxide and stearic acid are put into reactor A and outgased repeatedly and make reactor A be full of rare gas element, heating is fully dissolved Cadmium oxide; Cool to 60 ℃～30 ℃ then, add oxidation tri-n-octyl phosphine and cetylamine, after the degassing, stir again, be heated to 310-330 ℃, then among the storing solution injecting reactor A with selenium; Behind 300-260 ℃ of maintenance 3-10min, remove heating unit and make product be cooled to 220-180 ℃;
(c) with cadmium acetate or zinc acetate, oxidation tri-n-octyl phosphine and cetylamine are put into reactor B, are stirred and heated to 220-180 ℃ and keep more than the 30min after the degassing; Then the solution in the reactor B is transferred in the constant pressure funnel that is connected on the reactor A, again the sulfide storing solution is also transferred in this constant pressure funnel, stir, two portions solution is mixed after, slowly splash in the intensively stirred reactor A equably; Dropwise, lower the temperature and make solution temperature be stabilized in 120-90 ℃ keep 0.5-1.5h after, stop heating, make the solution cool to room temperature; In solution, add chloroform, centrifugal, discard upper strata suspended substance and lower sediment after, in solution, add methyl alcohol, leave standstill product is precipitated, centrifugal, remove behind the solution the CdSe/CdS of orange red flow-like or CdSe/ZnS resolution of precipitate in hexane, promptly get required quantum dot product; The product that obtains is the transparent salmon solution of hyperfluorescence.
As stated above, in the step (b) among the storing solution injecting reactor A with selenium; 300-260 ℃ keep 3-10min after, remove heating unit and make product be cooled to 30-50 ℃ earlier, take out the product (making the contrast sample) of a small amount of CdSe quantum dot with syringe after, remaining part is heated to 220-180 ℃; Carry out the operation of (c) step again.
The present invention is with mineral compound replaced C d (CH such as cadmium acetate or zinc acetates
3)
2, Zn (CH
3)
2Deng metallorganics, under gentle, safe relatively condition, prepared CdSe/CdS, II-VI core/shell type quantum dots such as CdSe/ZnS.Adopt the present invention to prepare the core/shell type quantum dot, materials safety is easy to get, and is cheap, and simple and safe operation does not need harsh appointed condition, makes the laboratory mass preparation become possibility.Product homogeneous and good monodispersity is arranged; Photoluminescent property is improved, and the 20-30% before quantum yield never coats brings up to 60-80%; Good stability.Such quantum dot can be used as the fluorescent mark material, is widely used in biological detection and analysis.
Description of drawings
Fig. 1 is the uv-visible absorption spectra of the CdSe quantum dot that makes with the present invention;
Fig. 2 is the uv-visible absorption spectra of the CdSe/CdS quantum dot that makes with the present invention;
Fig. 3 is the CdSe that makes with the present invention and the fluorescence spectrum of CdSe/CdS quantum dot;
Fig. 4 is the CdSe that makes with the present invention and the fluorescence spectrum of CdSe/ZnS quantum dot;
Fig. 5 is the EDX result of the SEM of the CdSe that makes with the present invention;
Fig. 6 is the EDX result of the SEM of the CdSe/CdS that makes with the present invention;
Fig. 7 is the TEM image of the CdSe quantum dot that makes with the present invention;
Fig. 8 is the TEM image of the CdSe/CdS quantum dot that makes with the present invention.
Embodiment
The preparation of CdSe/CdS or CdSe/ZnS core/shell type quantum dot is divided into two portions: (a) preparation of the single quantum dot of CdSe (b) makes the core/shell type quantum dot at CdSe outside coating CdS or ZnS.
The preparation of CdSe/CdS or CdSe/ZnS core/shell type quantum dot, comprise the steps: that specifically (a) is in glove box, the selenium powder of 0.1g is dissolved in the tri-n-octyl phosphine (TOP) and 2.1g dioctylamine of 0.54g, makes the storing solution of selenium, [(TMS) 50ul sulfuration two (trimethyl silyl)
2S] be dissolved in the tri-n-octyl phosphine (TOP) and 1.6g dioctylamine of 0.4g, make the storing solution of sulfide; (b) take by weighing 0.0165gCdO and 0.28g stearic acid and put into four-hole Schlenk reaction vessel A, adopt the Schlenk technology, charge into Ar gas after vacuumizing with vacuum pump, outgas so repeatedly six times so that be full of Ar gas in the reaction vessel, then be heated to 150 ℃ and keep about 25min, CdO is fully dissolved; Cool to then about 50 ℃, add 2.43g oxidation tri-n-octyl phosphine (TOPO) and 2.43g cetylamine (HDA), after adopting the degassing of Schlenk technology again, stir, be heated to 320 ℃, then from glove box, take out rapidly, it is injected reaction vessel with fast as far as possible speed with the storing solution of syringe with selenium in (a); After keeping 5min about 280 ℃, remove heating unit rapidly and make product be cooled to 30-50 ℃, promptly make the CdSe quantum dot, take out the product (making the contrast sample) of a small amount of CdSe quantum dot with syringe after, remaining part is heated to 200 ℃; (c) take by weighing 0.285g cadmium acetate (perhaps 0.0241g zinc acetate), 1.06gTOPO and 1.06gHDA put into three mouthfuls of Schlenk reaction vessel B, adopt to be stirred and heated to 200 ℃ and keep more than the 30min after the degassing of Schlenk technology; (d) with syringe the solution in (c) is transferred in the constant pressure funnel that is connected on the reaction vessel A, with syringe sulfide storing solution in (a) is transferred to from glove box in this constant pressure funnel again, stir by syringe, after two portions solution is mixed, splash into equably in the intensively stirred reactor A with per two seconds one speed; (e) dropwise, lower the temperature and make solution temperature be stabilized in 90 ℃ keep 1h after, stop heating, make the solution cool to room temperature; (f) in the solution of (e), add chloroform, centrifugal, after discarding upper strata suspended substance and lower sediment, in solution, add methyl alcohol, leaving standstill 1h precipitates product, centrifugal, remove behind the solution the CdSe/CdS of orange red flow-like or CdSe/ZnS resolution of precipitate in hexane, promptly get required CdSe/CdS or CdSe/ZnS quantum dot product; The product that obtains is the transparent salmon solution of hyperfluorescence.
Transmission electron microscope, scanning electron microscope, uv-visible absorption spectra, method characterization results such as fluorescence spectrum prove (referring to Fig. 1～Fig. 8), product homogeneous and good monodispersity is arranged; Photoluminescent property is improved, and the 20-30% before quantum yield never coats brings up to 60-80%; Good stability.
By the method for the invention, can make other II-VI core/shell type quantum dot.
Claims (1)
1. the preparation method of CdSe/CdS or CdSe/ZnS core/shell type quantum dot is characterized in that adopting following step:
(a) selenium powder is dissolved in tri-n-octyl phosphine and the dioctylamine, makes the storing solution of selenium, will vulcanize two (trimethyl silyl) and be dissolved in tri-n-octyl phosphine and the dioctylamine, make the storing solution of sulfide;
(b) Cadmium oxide and stearic acid are put into reactor A, the degassing makes reactor A be full of rare gas element repeatedly, and heating is fully dissolved Cadmium oxide; Cool to 60 ℃～30 ℃ then, add oxidation tri-n-octyl phosphine and cetylamine, after the degassing, stir again, be heated to 310-330 ℃, then among the storing solution injecting reactor A with selenium; Behind 300-260 ℃ of maintenance 3-10min, remove heating unit and make product be cooled to 220-180 ℃;
(c) with cadmium acetate or zinc acetate, oxidation tri-n-octyl phosphine and cetylamine are put into reactor B, are stirred and heated to 220-180 ℃ and keep more than the 30min after the degassing; Then the solution in the reactor B is transferred in the constant pressure funnel that is connected on the reactor A, again the sulfide storing solution is also transferred in this constant pressure funnel, stir, two portions solution is mixed after, slowly splash in the intensively stirred reactor A equably; Dropwise, lowering the temperature and making solution temperature be stabilized in 120-90 ℃ keeps stopping heating after 0.5-1.5 hour, makes the solution cool to room temperature; In solution, add chloroform, centrifugal, discard upper strata suspended substance and lower sediment after, in solution, add methyl alcohol, leave standstill product is precipitated, centrifugal, remove behind the solution the CdSe/CdS of orange red flow-like or CdSe/ZnS resolution of precipitate in hexane, promptly get required quantum dot product; The product that obtains is the transparent salmon solution of hyperfluorescence.
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| CNB021391521A CN1174080C (en) | 2002-10-10 | 2002-10-10 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
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| CNB021391521A CN1174080C (en) | 2002-10-10 | 2002-10-10 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
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| CN1174080C true CN1174080C (en) | 2004-11-03 |
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