CN101429433A - Nucleus-shell-shell structured quantum dot with high fluorescence quantum efficiency and method of producing the same - Google Patents
Nucleus-shell-shell structured quantum dot with high fluorescence quantum efficiency and method of producing the same Download PDFInfo
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- CN101429433A CN101429433A CNA2007100477970A CN200710047797A CN101429433A CN 101429433 A CN101429433 A CN 101429433A CN A2007100477970 A CNA2007100477970 A CN A2007100477970A CN 200710047797 A CN200710047797 A CN 200710047797A CN 101429433 A CN101429433 A CN 101429433A
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Abstract
The invention belongs to the technical field of nano material and biological analysis detection, and particularly discloses a method for preparing a high fluorescence quantum efficiency water soluble CdTe/CdS/Zns core-shell-shell structure quantum point by microwave. In water phase, zinc salt or zinc oxide is mixed with a water soluble sulfhydryl compound, and injected with pre-prepared CdTe/CdS core-shell structure quantum point solution to obtain CdTe/CdS/Zns precursor solution, and the precursor solution is placed in a glass pipe specially used for microwave radiation and subjected to microwave radiation reaction in a microwave reactor to obtain the CdTe/CdS/Zns core-shell-shell structure quantum point. The method is completely performed in the water phase, and is safe and convenient to operation. The obtain product has the advantages of high fluorescence quantum efficiency, good water solubility and excellent stability and biocompatibility, and can be widely applied to fluorescence labels for biological detection and analysis.
Description
Technical field
The present invention relates to nano material and bioanalysis detection technique field, be specifically related to a kind of high fluorescence quantum efficiency water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots and preparation method thereof.
Background technology
Quantum dot is a class by the elementary composition radius of II-VI family or III-V family less than or near the semiconductor nano crystal grain of exciton Bohr radius.Quantum dot has distinctive quantum size effect and surface effects, have many advantages with respect to traditional luminescent dye molecule with the nanocrystalline thing of marking: nanocrystalline exciting light spectrum width, emmission spectrum is narrow, symmetrical, the fluorescent emission wavelength can be by changing quantum dot size and component and being regulated, thereby the quantum dot of different size can be launched the fluorescence of different colours by the optical excitation of single wavelength, conveniently is used for the multi-color marking of multiple goal molecule.On the contrary, the fluorescence of multiple dyestuff but needs multiple laser to be excited, and this has not only increased experimental expenses, and makes analysis become complicated more.Nanocrystalline in addition luminous intensity height, photochemical stability is good, therefore quantum dot not only has purposes widely in optoelectronic information fields such as photoelectric device, photodiode, solid statelasers, and can be used as the novel fluorescent marker of a class, go out more and more tempting application prospect in biomedical fields such as molecular biology, immunobiology, clinical medicine.
The semiconductor nano crystal grain that needs in the practical application must have good luminescent properties (luminous efficiency height, fluorescence spectrum half-peak width), semiconductor nano crystal grain is applied to biomarker, also requires it to have good light stability and biocompatibility.Therefore, the water-soluble quantum dot that processability is good becomes hot research in recent years.Method by microwave radiation can successfully prepare the good water-soluble CdTe quantum dots of spectrum property (Li L, et.Chem.Comm, 2005,528-530 at present; He Y, et.J.Phy.Chem.B, 2006,110,13352-13356; He Y, et.Chem.Mater, 2007,19,359-365) with CdTe/CdS nucleocapsid structure quantum dot (He Y, et.J.Phy.Chem.B, 2006,110,13370-13373; ).But therefore CdTe quantum dot for preparing and CdTe/CdS nucleocapsid structure quantum dot have very serious cytotoxicity because there is the heavy metal Cd particle in the surface.Can be in quantum dot surface epitaxy one deck lattice constant match, the wideer ZnS inorganic materials of band gap, because Zn has excellent biological compatibility, therefore can weaken the cytotoxicity of quantum dot to a great extent, improve the cell biological consistency of quantum dot.At present about the report of this respect only limit to the organic phase method (TalapinD.V., et.J.Phys.Chem.B 2004,118,18826-18831.), but the preparation condition harshness, reactions steps complexity, cost height.
Therefore, this area presses for the quantum dot that a kind of CdTe/CdS/ZnS of having nuclear-shell-shell structure is provided, and described quantum dot should be able to have good water dispersible, stability, spectrum property and excellent biocompatibility concurrently; And need provide the simple and convenient process for preparing of this quantum dot.
Summary of the invention
The present invention aims to provide the quantum dot of a kind of CdTe/CdS/ZnS of having nuclear-shell-shell structure.
Second purpose of the present invention provides the preparation method of described CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
The 3rd purpose of the present invention provides the purposes of described CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
In a first aspect of the present invention, a kind of water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is provided, its fluorescence emission peak λ max is 510-650nm.More preferably, its fluorescence emission peak λ max is 520-620nm.
In another preference, the fluorescence spectrum emission peak halfwidth of described water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is 30-70nm.More preferably, its fluorescence spectrum emission peak halfwidth is 35-60nm.
In another preference, the fluorescence quantum yield of described water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is 10-90%.More preferably, its fluorescence quantum yield is 30-80%.
In a second aspect of the present invention, a kind of preparation method as above-mentioned CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is provided, described method comprises step:
(1) is that 0.0005-0.1mol/L of 7.5-13 contains in the solution of the oxide compound of zinc salt or zinc and water-soluble sulfhydryl compound and sulfosalt in the pH value, adds water-soluble CdTe/CdS nucleocapsid structure quantum dot, obtain the CdTe/CdS/ZnS precursor solution;
(2) the CdTe/CdS/ZnS precursor solution that step (1) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 50-150 ℃ of Heating temperatures obtain as above-mentioned water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
In another preference, in step (1): raw material zinc source, sulfhydryl compound, sulphur source, CdTe/CdS quantum dot are Zn in molar ratio
2+: sulfhydryl compound: S
2-: CdTe/CdS=1:(1.5-8): (0.3-0.9): (0.05-3).
In another preference, described method comprises step:
(a) preparation is as the sodium hydrogen telluride (NaHTe) or hydrogen telluride potassium (KHTe) solution in tellurium source: with mol ratio is the sodium borohydride (NaBH of 1.5-5:1
4) or POTASSIUM BOROHYDRIDE (KBH
4) and tellurium powder (Te) left standstill 7-30 hours at water in 0-30 ℃, obtain sodium hydrogen telluride or hydrogen telluride potassium solution;
(b) be that logical nitrogen removes oxygen in the solution of 0.0005-0.1mol/L of 7-13 oxide compound, oxyhydroxide and water-soluble sulfhydryl compound of containing cadmium salt or cadmium in the pH value, the sodium hydrogen telluride or the hydrogen telluride potassium solution that obtain at 70-120 ℃ of implantation steps (a), reacted 1-40 hours, and obtained the CdTe quantum dot solution;
(c) be the CdTe quantum dot solution that implantation step (b) obtains in the solution of 0.0005-0.1mol/L of 7-13 oxide compound, oxyhydroxide and water-soluble sulfhydryl compound and sulfosalt of containing cadmium salt or cadmium in the pH value, obtain the CdTe/CdS precursor solution;
(d) the CdTe/CdS precursor solution that step (c) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 70-200 ℃ of Heating temperatures obtain water-soluble CdTe/CdS nucleocapsid structure quantum dot;
(e) be that 0.0005-0.1mol/L of 7.5-13 contains in the solution of the oxide compound of zinc salt or zinc and water-soluble sulfhydryl compound and sulfosalt in the pH value, add water-soluble CdTe/CdS nucleocapsid structure quantum dot that step (d) obtains, obtain the CdTe/CdS/ZnS precursor solution;
(f) the CdTe/CdS/ZnS precursor solution that step (e) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 50-150 ℃ of Heating temperatures obtain as above-mentioned water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
In another preference, in step (b): raw material cadmium source, sulfhydryl compound, tellurium source are Cd in molar ratio
2+: sulfhydryl compound: Te
-=1:(1.5-5): (0.3-0.7).
In another preference, in the step (c): raw material cadmium source, sulfhydryl compound, sulphur source, CdTe quantum dot are Cd in molar ratio
2+: sulfhydryl compound: S
2-: CdTe=1:(1.5-8): (0.3-0.9): (0.05-3).
In another preference, oxide compound, the oxyhydroxide of described cadmium salt or cadmium comprise: Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate; The oxide compound of zinc salt or zinc comprises: zinc chloride, zinc iodide, zinc bromide, zinc oxide, zinc sulfate, zinc carbonate, zinc acetate or zinc nitrate; Described water miscible sulfhydryl compound comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol; Described sulfosalt comprises sodium sulphite or potassium sulphide.
In a third aspect of the present invention, provide a kind of as the above-mentioned water-soluble CdTe/application of CdS/ZnS nuclear-shell-core-shell structure quantum dots in bioanalysis chemistry and/or molecular biology.
In view of the above, the invention provides the quantum dot of a kind of CdTe/CdS/ZnS of having nuclear-shell-shell structure, described quantum dot should be able to have good water dispersible, stability, spectrum property and excellent biocompatibility concurrently; The present invention also provides the simple and convenient process for preparing of this quantum dot.
Description of drawings
Fig. 1 has shown the ultraviolet-fluorescence spectrum of the CdTe quantum dot, CdTe/CdS nucleocapsid structure quantum dot and the CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots that prepare with the present invention.
The light field transmission electron microscope (TEM) that Fig. 2 has shown CdTe quantum dot provided by the invention, CdTe/CdS nucleocapsid structure quantum dot and CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots as and high resolution bright field micrograph transmission electron microscope (HRTEM) as;
Wherein, a, b and c are respectively the CdTe quantum dots, the TEM picture of CdTe/CdS nucleocapsid structure quantum dot and CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots, and wherein white scale is represented 20 nanometers; D, e and f are respectively the CdTe quantum dots, the HRTEM picture of CdTe/CdS nucleocapsid structure quantum dot and CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots, and wherein white scale is represented 5 nanometers.
Embodiment
The contriver is through extensive and deep research, found a kind of method at the directly synthetic CdTe/CdS/ZnS nuclear-shell of aqueous phase-core-shell structure quantum dots, described method is to be stablizer with water-soluble sulfhydryl compound, in the solution of oxide compound that contains zinc salt or zinc and sulfosalt, under the condition of pH7.5-13, add water-soluble CdTe/CdS nucleocapsid structure quantum dot and obtain the CdTe/CdS/ZnS precursor solution; Again resulting CdTe/CdS/ZnS precursor solution is carried out microwave treatment and obtain water-soluble CdTe provided by the invention/CdS/ZnS nuclear-shell-core-shell structure quantum dots.CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots that the present invention obtains has good water dispersible, stability, spectrum property and excellent biocompatibility.
The fluorescence emission peak λ max of CdTe/CdS/ZnS nuclear-shell provided by the invention-core-shell structure quantum dots is 510-650nm, preferably is 520-620nm; Its fluorescence spectrum emission peak halfwidth is 30-70nm, preferably is 35-60nm; Its fluorescence quantum yield is 10-90%, preferably is 30-80%.
The present invention also provides a kind of operational safety, the microwave preparation of high fluorescence quantum efficiency water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots easily, and described method comprises step:
(1) is that 0.0005-0.1mol/L of 7.5-13 contains in the solution of the oxide compound of zinc salt or zinc and water-soluble sulfhydryl compound and sulfosalt in the pH value, adds water-soluble CdTe/CdS nucleocapsid structure quantum dot, obtain the CdTe/CdS/ZnS precursor solution;
(2) the CdTe/CdS/ZnS precursor solution that step (1) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 50-150 ℃ of Heating temperatures obtain as above-mentioned water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
In another preference, method provided by the invention comprises following concrete steps:
1, preparation is as the sodium hydrogen telluride NaHTe or the hydrogen telluride potassium KHTe solution in tellurium source: with mol ratio is the sodium borohydride NaBH of 1.5:1 to 5:1
4Or POTASSIUM BOROHYDRIDE KBH
4Te places water with the tellurium powder, 0-30 ℃ of following standing and reacting 7-30 hours, obtains NaHTe or hydrogen telluride potassium KHTe solution;
2, preparation 0.0005-0.1mol/L is as the cadmium salt in cadmium source or oxide compound, oxyhydroxide and the water-soluble sulfhydryl compound solution of cadmium, the pH value to 7-13 of regulator solution, logical nitrogen removes oxygen, be heated to 70-120 ℃, inject NaHTe or KHTe solution, reacted 1-40 hours, and obtained the CdTe quantum dot;
3, the concentration that water-soluble sulfhydryl compound is added as the cadmium source is oxide compound, oxyhydroxide and the sulfosalt solution of 0.0005-0.1mol/L cadmium salt or cadmium, and the pH value to 7-13 of regulator solution is injected the CdTe quantum dot, obtains the CdTe/CdS precursor solution;
4, the CdTe/CdS precursor solution is carried out microwave preparation, precursor solution is placed the microwave radiation special glass tube, in microwave reactor, carry out the microwave radiation reaction, can obtain water-soluble CdTe/CdS core/shell type quantum dot.Wherein, microwave heating condition is: microwave power 15W-1000W, heat-up times 30 second-1 hour, 70-200 ℃ of Heating temperatures;
5, the concentration that water-soluble sulfhydryl compound is added as the zinc source is the oxide compound and the sulfosalt solution of 0.0005-0.1mol/L zinc salt or zinc, the pH value to 7.5-13 of regulator solution, inject CdTe/CdS core/shell type quantum dot, obtain the CdTe/CdS/ZnS precursor solution;
6, the CdTe/CdS/ZnS precursor solution is carried out microwave preparation, precursor solution is placed the microwave radiation special glass tube, in microwave reactor, carry out the microwave radiation reaction, can obtain water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.Wherein, microwave heating condition is: microwave power 15W-1000W, heat-up times 30 second-1 hour, 50-150 ℃ of Heating temperatures;
In the step 2 of aforesaid method, raw material cadmium source, sulfhydryl compound, tellurium source are Cd in molar ratio
2+: sulfhydryl compound: HTe
-=1:(1.5-5): (0.3-0.7).
In the step 3 of aforesaid method, raw material cadmium source, sulfhydryl compound, sulphur source, cadmium telluride quantum dot are Cd in molar ratio
2+: sulfhydryl compound: S
2-: CdTe=1:(1.5-8): (0.3-0.9): (0.05-3).
In the step 5 of aforesaid method, raw material zinc source, sulfhydryl compound, sulphur source, cadmium telluride/cadmiumsulfide quantum dot are Zn in molar ratio
2+: sulfhydryl compound: S
2-: CdTe/CdS=1:(1.5-8): (0.3-0.9): (0.05-3).
Oxide compound, the oxyhydroxide of cadmium salt of the present invention or cadmium comprise: Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate; The oxide compound of zinc salt or cadmium comprises: zinc chloride, zinc iodide, zinc bromide, zinc oxide, zinc sulfate, zinc carbonate, zinc acetate, zinc nitrate; Described water miscible sulfhydryl compound comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol; Described sulfosalt comprises sodium sulphite or potassium sulphide.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets is disclosed can with any composition forms and usefulness, each feature that is disclosed in the specification sheets can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore removing has special instruction, and the feature that is disclosed only is the general example of equalization or similar features.
Major advantage of the present invention is:
1, carry out at aqueous phase fully, operational safety, easy rapidly, raw material is easy to get;
2, water-soluble CdTe provided by the invention/CdS/ZnS nuclear-shell-core-shell structure quantum dots has high fluorescence quantum efficiency simultaneously concurrently, excellent light stability and biocompatibility, and have good water-solubility, can be used as fluorescence labeling probe and be widely used in biological detection and analysis.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all per-cent and umber by weight.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
Embodiment 1
Preparation CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots I
(1) sodium hydrogen telluride preparation:
With 98 milligrams of NaBH
4Solid and 115.6 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain NaHTe solution in reaction under 15 ℃ after 11 hours, and are standby;
(2) CdTe quantum dot preparation
With 25.0 milligrams of CdCl
2Be dissolved in 100 ml waters, add 0.02 milliliter of Thiovanic acid, regulate pH=10.5 with the NaOH solution of 0.5 mol, logical nitrogen 30 minutes is warming up to 100 ℃, injects 0.2 milliliter of NaHTe solution, reacts 3.5 hours, obtains the CdTe quantum dot solution;
(3) CdTe/CdS precursor solution preparation
With 16.5 milligrams of CdCl
2With 3.6 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.01 milliliter of Thiovanic acid, regulates pH=10.5 with the NaOH appearance of 0.5 mol, injects 10 milliliters of CdTe quantum dot solutions, obtains the CdTe/CdS precursor solution;
(4) microwave radiation prepares CdTe/CdS core/shell structure quantum dot
Resulting CdTe/CdS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS core/shell structure quantum dot.The microwave radiation condition is as follows: microwave power: 50W; Temperature of reaction: 100 ℃; Reaction times: 15mins;
(5) CdTe/CdS/ZnS precursor solution preparation
With 8.2 milligrams of CdCl
2With 3.9 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.02 milliliter of Thiovanic acid, regulates pH=9.0 with the NaOH appearance of 0.5 mol, injects 20 milliliters of CdTe/CdS core/shell type quantum dots, obtains the CdTe/CdS/ZnS precursor solution;
(6) microwave radiation prepares CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots I
Resulting CdTe/CdS/ZnS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.The microwave radiation condition is as follows: microwave power: 30W; Temperature of reaction: 70 ℃; Reaction times: 10mins.
CdTe/CdS/ZnS nuclear-the shell for preparing-core-shell structure quantum dots I fluorescence emission peak λ max is 550-560nm; Fluorescence quantum efficiency is 70-85%; Halfwidth is 33-38nm.
Embodiment 2
Preparation CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots II
(1) hydrogen telluride potassium preparation:
With 83.5 milligrams of KBH
4Solid and 92.6 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain KHTe solution in reaction under 10 ℃ after 15 hours, and are standby;
(2) CdTe quantum dot preparation
With 26.9 milligrams of CdCl
2Be dissolved in 100 ml waters, add 0.07 milliliter of Thiovanic acid, regulate pH=11.0 with the NaOH solution of 0.5 mol, logical nitrogen 30 minutes is warming up to 100 ℃, injects 0.2 milliliter of KHTe solution, reacts 5 hours, obtains the CdTe quantum dot solution;
(3) CdTe/CdS precursor solution preparation
With 30.5 milligrams of CdCl
2With 7.8 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.05 milliliter of Thiovanic acid, regulates pH=7.5 with the NaOH appearance of 0.5 mol, injects 10 milliliters of CdTe quantum dot solutions, obtains the CdTe/CdS precursor solution;
(4) microwave radiation prepares CdTe/CdS core/shell type quantum dot
Resulting CdTe/CdS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS core/shell type quantum dot.The microwave radiation condition is as follows: microwave power: 15W; Temperature: 80 ℃; First program time: 35mins;
(5) CdTe/CdS/ZnS precursor solution preparation
With 16.8 milligrams of CdCl
2With 9.5 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.08 milliliter of Thiovanic acid, regulates pH=10.0 with the NaOH appearance of 0.5 mol, injects 20 milliliters of CdTe/CdS core/shell type quantum dots, obtains the CdTe/CdS/ZnS precursor solution;
(6) microwave radiation prepares CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots II
Resulting CdTe/CdS/ZnS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.The microwave radiation condition is as follows: microwave power: 50W; Temperature of reaction: 70 ℃; Reaction times: 50mins.
CdTe/CdS/ZnS nuclear-the shell for preparing-core-shell structure quantum dots I fluorescence emission peak λ max is 600-610nm; Fluorescence quantum efficiency is 15-20%; Halfwidth is 60-65nm.
Embodiment 3
Preparation CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots III
(1). the sodium hydrogen telluride preparation
With 90.7 milligrams of NaBH
4Solid and 127.6 milligrams of Te powder are put in the little flask, add 2.5 ml waters, can obtain NaHTe solution in reaction under 0 ℃ after 8 hours, and are standby;
(2) CdTe quantum dot preparation
With 30.0 milligrams of CdCl
2Be dissolved in 100 ml waters, add 0.05 milliliter of Thiovanic acid, regulate pH=9.0 with the NaOH solution of 0.5 mol, logical nitrogen 30 minutes is warming up to 100 ℃, injects 0.25 milliliter of NaHTe solution, reacts 5 hours, obtains the CdTe quantum dot solution;
(3) CdTe/CdS precursor solution preparation
With 25.9 milligrams of CdCl
2With 3.9 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.03 milliliter of Thiovanic acid, regulates pH=8 with the NaOH solution of 0.5 mol, injects 20 milliliters of CdTe quantum dot solutions, obtains the CdTe/CdS precursor solution;
(4) the program controlling microwave radiation prepares CdTe/CdS core/shell type quantum dot
Resulting CdTe/CdS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS core/shell type quantum dot.The microwave radiation condition is as follows: microwave power: 300W; Temperature: 140 ℃; First program time: 1mins;
(5) CdTe/CdS/ZnS precursor solution preparation
With 13.2 milligrams of CdCl
2With 4.5 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.03 milliliter of Thiovanic acid, regulates pH=8.4 with the NaOH appearance of 0.5 mol, injects 20 milliliters of CdTe/CdS core/shell type quantum dots, obtains the CdTe/CdS/ZnS precursor solution;
(6) microwave radiation prepares CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots III
Resulting CdTe/CdS/ZnS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.The microwave radiation condition is as follows: microwave power: 50W; Temperature of reaction: 100 ℃; Reaction times: 3mins.
CdTe/CdS/ZnS nuclear-the shell for preparing-core-shell structure quantum dots I fluorescence emission peak λ max is 565-575nm; Fluorescence quantum efficiency is 30-35%; Halfwidth is 50-55nm.
Embodiment 4
Preparation CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots IV
(1) sodium hydrogen telluride preparation:
With 90.5 milligrams of NaBH
4Solid and 91.2 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain NaHTe solution in reaction under 10 ℃ after 10 hours, and are standby;
(2) CdTe quantum dot preparation
With 22.5 milligrams of CdCl
2Be dissolved in 100 ml waters, add 0.03 milliliter of Thiovanic acid, regulate pH=9.5 with the NaOH solution of 0.5 mol, logical nitrogen 30 minutes is warming up to 100 ℃, injects 0.2 milliliter of NaHTe solution, reacts 3 hours, obtains the CdTe quantum dot solution;
(3) CdTe/CdS precursor solution preparation
With 18.5 milligrams of CdCl
2With 5.6 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.06 milliliter of Thiovanic acid, regulates pH=10.5 with the NaOH appearance of 0.5 mol, injects 10 milliliters of CdTe quantum dot solutions, obtains the CdTe/CdS precursor solution;
(4) microwave radiation prepares CdTe/CdS core/shell type quantum dot
Resulting CdTe/CdS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS core/shell type quantum dot.The microwave radiation condition is as follows: microwave power: 50W; Temperature: 100 ℃; First program time: 5mins;
(5) CdTe/CdS/ZnS precursor solution preparation
With 10.0 milligrams of CdCl
2With 5.8 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.07 milliliter of Thiovanic acid, regulates pH=9.5 with the NaOH appearance of 0.5 mol, injects 20 milliliters of CdTe/CdS core/shell type quantum dots, obtains the CdTe/CdS/ZnS precursor solution;
(6) microwave radiation prepares CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots IV
Resulting CdTe/CdS/ZnS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.The microwave radiation condition is as follows: microwave power: 50W; Temperature of reaction: 90 ℃; Reaction times: 3mins.
CdTe/CdS/ZnS nuclear-the shell for preparing-core-shell structure quantum dots I fluorescence emission peak λ max is 525-535nm; Fluorescence quantum efficiency is 35-40%; Halfwidth is 40-45nm.
Embodiment 5
Preparation CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots V
(1) hydrogen telluride potassium preparation
With 50.8 milligrams of KBH
4Solid and 63.8 milligrams of Te powder are put in the little flask, add 2 ml waters, can obtain KHTe solution in reaction under 20 ℃ after 15 hours, and are standby;
(2) CdTe quantum dot preparation
With 25.6 milligrams of CdCl
2Be dissolved in 100 ml waters, add 0.018 milliliter of Thiovanic acid, regulate pH=8.5 with the NaOH solution of 0.5 mol, logical nitrogen 30 minutes is warming up to 90 ℃, injects 0.3 milliliter of KHTe solution, reacts 10 hours, obtains the CdTe quantum dot solution;
(3) CdTe/CdS precursor solution preparation
With 15.5 milligrams of CdCl
2With 5.0 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.02 milliliter of Thiovanic acid, regulates pH=9.5 with the NaOH solution of 0.5 mol, injects 15 milliliters of CdTe quantum dot solutions, obtains the CdTe/CdS precursor solution;
(4) the program controlling microwave radiation prepares CdTe/CdS core/shell type quantum dot
Resulting CdTe/CdS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS core/shell type quantum dot.The microwave radiation condition is as follows: microwave power: 100W; Temperature: 120 ℃; First program time: 3mins;
(5) CdTe/CdS/ZnS precursor solution preparation
With 7.8 milligrams of CdCl
2With 4.5 milligrams of Na
2S is dissolved in 100 ml waters, adds 0.03 milliliter of Thiovanic acid, regulates pH=9.0 with the NaOH appearance of 0.5 mol, injects 20 milliliters of CdTe/CdS core/shell type quantum dots, obtains the CdTe/CdS/ZnS precursor solution;
(6) microwave radiation prepares CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots V
Resulting CdTe/CdS/ZnS precursor solution is carried out the microwave radiation preparation, can obtain CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots.The microwave radiation condition is as follows: microwave power: 50W; Temperature of reaction: 60 ℃; Reaction times: 20mins.
CdTe/CdS/ZnS nuclear-the shell for preparing-core-shell structure quantum dots I fluorescence emission peak λ max is 545-550nm; Fluorescence quantum efficiency is 50-55%; Halfwidth is 35-40nm.
Embodiment 6
Purposes embodiment
(Hela) cell is drawn in CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots I specific mark sea
Hela cell kind to the cover glass of anticipating, is cleaned cell 3 times with fresh culture; Under 37 ℃ of conditions, cell and vitamin H-Toxins,exo-, cholera albumen were hatched 20 minutes altogether; Clean cell 3 times with fresh culture; Under 37 ℃ of conditions, above-mentioned cell and microbiotic-CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots were hatched 30 minutes altogether, and described CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots I that embodiment 1 prepares; Cover glass is taken out, and the cover that growth has cell is then gone up fluorescent microscope and is detected to the slide glass of anticipating.Can observe CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots I specific marker to the HeLa cell surface, be yellow green light.
By the method for the invention, can prepare the water-soluble CdTe/CdS/ZnS nuclear-shell-shell type quantum point of other type-stable agent.Described stablizer comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (13)
1. water-soluble CdTe/CdS/ZnS nuclear-shell-core-shell structure quantum dots is characterized in that, its fluorescence emission peak λ max is 510-650nm.
2. quantum dot as claimed in claim 1 is characterized in that, its fluorescence emission peak λ max is 520-620nm.
3. quantum dot as claimed in claim 1 is characterized in that, its fluorescence spectrum emission peak halfwidth is 30-70nm.
4. quantum dot as claimed in claim 1 is characterized in that, its fluorescence spectrum emission peak halfwidth is 35-60nm.
5. quantum dot as claimed in claim 1 is characterized in that, its fluorescence quantum yield is 10-90%.
6. quantum dot as claimed in claim 1 is characterized in that, its fluorescence quantum yield is 30-80%.
7. the preparation method of CdTe/CdS/ZnS nuclear-shell as claimed in claim 1-core-shell structure quantum dots is characterized in that, described method comprises step:
(1) is that 0.0005-0.1mol/L of 7.5-13 contains in the solution of the oxide compound of zinc salt or zinc and water-soluble sulfhydryl compound and sulfosalt in the pH value, adds water-soluble CdTe/CdS nucleocapsid structure quantum dot, obtain the CdTe/CdS/ZnS precursor solution;
(2) the CdTe/CdS/ZnS precursor solution that step (1) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 50-150 ℃ of Heating temperatures obtain water-soluble CdTe as claimed in claim 1/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
8. preparation method as claimed in claim 7 is characterized in that, in step (1): raw material zinc source, sulfhydryl compound, sulphur source, CdTe/CdS quantum dot are Zn in molar ratio
2+: sulfhydryl compound: S
2-: CdTe/CdS=1:(1.5-8): (0.3-0.9): (0.05-3).
9. preparation method as claimed in claim 7 is characterized in that, described method comprises step:
(a) preparation is as the sodium hydrogen telluride or the hydrogen telluride potassium solution in tellurium source: with mol ratio is that the sodium borohydride of 1.5-5:1 or POTASSIUM BOROHYDRIDE and tellurium powder left standstill 7-30 hours at water in 0-30 ℃, obtains sodium hydrogen telluride or hydrogen telluride potassium solution;
(b) be that logical nitrogen removes oxygen in the solution of 0.0005-0.1mol/L of 7-13 oxide compound, oxyhydroxide and water-soluble sulfhydryl compound of containing cadmium salt or cadmium in the pH value, the sodium hydrogen telluride or the hydrogen telluride potassium solution that obtain at 70-120 ℃ of implantation steps (a), reacted 1-40 hours, and obtained the CdTe quantum dot solution;
(c) be the CdTe quantum dot solution that implantation step (b) obtains in the solution of 0.0005-0.1mol/L of 7-13 oxide compound, oxyhydroxide and water-soluble sulfhydryl compound and sulfosalt of containing cadmium salt or cadmium in the pH value, obtain the CdTe/CdS precursor solution;
(d) the CdTe/CdS precursor solution that step (c) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 70-200 ℃ of Heating temperatures obtain water-soluble CdTe/CdS nucleocapsid structure quantum dot;
(e) be that 0.0005-0.1mol/L of 7.5-13 contains in the solution of the oxide compound of zinc salt or zinc and water-soluble sulfhydryl compound and sulfosalt in the pH value, add water-soluble CdTe/CdS nucleocapsid structure quantum dot that step (d) obtains, obtain the CdTe/CdS/ZnS precursor solution;
(f) the CdTe/CdS/ZnS precursor solution that step (e) is obtained carries out microwave preparation, described microwave heating condition is: microwave power 15-1000W, 30 seconds-1 hour heat-up time, 50-150 ℃ of Heating temperatures obtain water-soluble CdTe as claimed in claim 1/CdS/ZnS nuclear-shell-core-shell structure quantum dots.
10. method as claimed in claim 9 is characterized in that, in step (b): raw material cadmium source, sulfhydryl compound, tellurium source are Cd in molar ratio
2+: sulfhydryl compound: Te
-=1:(1.5-5): (0.3-0.7).
11. method as claimed in claim 9 is characterized in that, in the step (c): raw material cadmium source, sulfhydryl compound, sulphur source, CdTe quantum dot are Cd in molar ratio
2+: sulfhydryl compound: S
2-: CdTe=1:(1.5-8): (0.3-0.9): (0.05-3).
12. as the arbitrary described method of claim 7-11, it is characterized in that oxide compound, the oxyhydroxide of described cadmium salt or cadmium comprise: Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate; The oxide compound of zinc salt or zinc comprises: zinc chloride, zinc iodide, zinc bromide, zinc oxide, zinc sulfate, zinc carbonate, zinc acetate or zinc nitrate; Described water miscible sulfhydryl compound comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol; Described sulfosalt comprises sodium sulphite or potassium sulphide.
13. the water-soluble CdTe as claimed in claim 1/application of CdS/ZnS nuclear-shell-core-shell structure quantum dots in bioanalysis chemistry and/or molecular biology.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104174863A (en) * | 2013-05-21 | 2014-12-03 | 国家纳米科学中心 | Germanium nano cluster and preparation method and application thereof |
| CN104610971A (en) * | 2014-05-06 | 2015-05-13 | 上海大学 | Aqueous-phase preparation method of ZnTe quantum dots with high fluorescence yield |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104174863A (en) * | 2013-05-21 | 2014-12-03 | 国家纳米科学中心 | Germanium nano cluster and preparation method and application thereof |
| CN104174863B (en) * | 2013-05-21 | 2016-08-10 | 国家纳米科学中心 | A kind of germanium nanocluster, Its Preparation Method And Use |
| CN104610971A (en) * | 2014-05-06 | 2015-05-13 | 上海大学 | Aqueous-phase preparation method of ZnTe quantum dots with high fluorescence yield |
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