CN104477858A - Method for synthesizing controllable-luminescence CdSe bare nucleus quantum dots by using microfluids - Google Patents
Method for synthesizing controllable-luminescence CdSe bare nucleus quantum dots by using microfluids Download PDFInfo
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- CN104477858A CN104477858A CN201410736143.9A CN201410736143A CN104477858A CN 104477858 A CN104477858 A CN 104477858A CN 201410736143 A CN201410736143 A CN 201410736143A CN 104477858 A CN104477858 A CN 104477858A
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- C01—INORGANIC CHEMISTRY
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
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Abstract
The invention relates to a method for synthesizing controllable-luminescence CdSe bare nucleus quantum dots by using microfluids, which comprises the following steps: mixing a cadmium precursor solution and a selenium precursor solution, introducing into polytetrafluoroethylene capillaries, reacting in an oil bath, washing, centrifugating, and dispersing to obtain the CdSe bare nucleus quantum dots. The micro-reaction synthesis time is controlled to accurately control the size of the reaction product quantum dots, thereby obtaining the semiconductor quantum dot material with higher purity, uniform size, favorable dispersity, controllable luminescence and high quantum efficiency. The method has the advantages of mild experimental conditions and simple experimental operation; the obtained product has high yield and purity; and the generation of the product can be controlled by controlling the reaction time, temperature and other conditions. The method promotes the practical application of the semiconductor nano material, and can be applied to the fields of photoelectric materials, biomarkers and the like in a better and wider way.
Description
Technical field
The invention belongs to the preparation field of CdSe bare nucleus quantum dot, particularly the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties is controlled.
Background technology
Be subject to quantum dot (the Quantum Dots of extensive concern in recent years, QDs) owing to having excitation spectrum bandwidth, emission band is narrow, emission wavelength is adjustable, fluorescence quantum yield is high and the photochemical stability excellent optical characteristics such as good, to become in biological fluorescent labelling and Chemical Luminescent Probes very one of fluorescent material having development potentiality.Functional modification is carried out to quantum dot surface, not only can be used for and biomolecule action, also can be applicable to the detection analysis of the environmental pollutant such as heavy metal ion.Wherein CdSe quantum dot is that people study quantum dot the most widely.Its emission wavelength is with size adjustable, and spectral range can cover the whole visible region of ruddiness from blue light, and has and very wide excite scope and narrow transmitting peak width, and quantum yield is also relatively high.Semiconductor-quantum-point has the humorous optico-electronic properties of size adjustable, has been widely used in photodiode, solar cell and biological fluorescent labelling.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for the controlled CdSe bare nucleus quantum dot of a kind of microfluid synthesis luminescent properties, wherein the emission wavelength range of CdSe quantum dot of the present invention is at 485nm ~ 610nm nm, and by the adjustment of reaction times and temperature, Effective Regulation being carried out to it, its fluorescence quantum yield reaches 87%.
The method of the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties of the present invention is controlled, comprising:
(1) be dissolved in solvent by Cadmium oxide, nitrogen protection, 300 DEG C of stirrings, obtain cadmium precursor solution;
(2) selenium is dissolved in solvent, stirring at room temperature, obtains selenium precursor solution;
(3) by cadmium precursor solution and the mixing of selenium precursor solution, pass in polytetrafluoroethylene capillary, pass through oil bath without the need under atmosphere protection, reaction, then must to wash containing the mixing solutions of CdSe quantum dot, centrifugal, CdSe Colloidal Quantum Dots precipitates, and dispersion, to obtain final product; Wherein the volume ratio of selenium precursor solution and cadmium precursor solution is 10:1 ~ 1:10.
In described step (1), solvent is the mixing solutions of 1-octadecylene and oleic acid.
The volume ratio of described 1-octadecylene and oleic acid is 1:2-1:10.
In described step (1), the concentration of cadmium precursor solution is 0.1-1.0mmol/mL.
In described step (2), solvent is tri octyl phosphine TOP.
In described step (2), the concentration of selenium precursor solution is 0.1-1.0mmol/mL.
In described step (3), temperature of reaction is 200-250 DEG C, and the reaction times is 2s-200s.
In described step (3), washing is for using washing with acetone 1-5 time, and the time is greater than 10min, and centrifugal rotational speed is 6000-9000r/min, centrifugation time 20-25min.
Described step is separated in (3): be dispersed in toluene or normal hexane.
The emission wavelength of described CdSe quantum dot is at 485nm ~ 610nm, and quantum yield reaches 48% ~ 87%, and halfwidth is 17nm ~ 30nm.
Whole reaction process of the present invention, reaction vessel is the polytetrafluoroethylene capillary being communicated with syringe and advancing, and accurately can control the reaction times and obtain size uniform, the Colloidal Quantum Dots that luminescent properties is concentrated, and is convenient to the dispersion of quantum dot and luminous regulation and control.
Because nano material has large specific surface area, such reaction unit is adopted to control, without the need to N
2gas is protected, and nano material in preparation can be prevented equally to be oxidized.
The present invention adopts a kind of simple gentle method preparing the controlled CdSe quantum dot of luminescent properties of chemistry experiment operating, prepare fluorescence emission peak and cover the Colloidal Quantum Dots solution of blue light to red light region, and quantum dot light emitting halfwidth is narrower, about 17nm can be reached, quantum yield is high, and the quantum yield being positioned at the quantum dot in orange light region reaches as high as 87%.The present invention prepares Se presoma and Cd presoma respectively, required and require to control reaction conditions with the method for most simple operations according to individual, achieve and adopt safe and simple experimental technique to obtain polymolecularity and the size bare nucleus CdSe quantum dot that luminescent properties is controlled all.
beneficial effect
The present invention is directed to the major defect of CdSe quantum dot preparation method in prior art, by the presoma of difference building-up reactions thing, the size of quantum dot is selectively synthesized by external control reaction conditions, the present invention is adopted to prepare CdSe quantum dot, good dispersity, purity are high, size uniform easily controls, and luminous efficiency, quantum yield is high;
The emission wavelength range of CdSe quantum dot of the present invention at 485nm ~ 610nm nm, and carries out Effective Regulation by the adjustment of reaction times and temperature to it, and its fluorescence quantum yield reaches 87%;
CdSe quantum dot prepared by the present invention is expected to be applied in LED, bioprobe, in photoelectric device.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the CdSe quantum dot of embodiment 1;
Fig. 2 is the absorption spectrum of the CdSe quantum dot of embodiment 1;
Fig. 3 is the fluorescent emission collection of illustrative plates of the CdSe quantum dot of embodiment 1;
Fig. 4 is the HRTEM collection of illustrative plates of the CdSe quantum dot of embodiment 1;
Fig. 5 is CdSe quantum dot luminous digital photograph under UV-irradiation of embodiment 1; Wherein a is under UV-irradiation, and b is under natural light;
Fig. 6 is the absorption spectrum of the CdSe quantum dot of embodiment 2;
Fig. 7 is the fluorescent emission collection of illustrative plates of the CdSe quantum dot of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) preparation of Se presoma:
Be dissolved in by 0.005mol selenium powder in 10mL trimethyl-phosphine (TOP), dispersion is stirred to the Se-TOP precursor solution forming evenly clarification;
(2) preparation of Cd presoma:
1-octadecylene mixes with 5: 1 with oleic acid volume, adds in Cadmium oxide 0.005mol to above-mentioned mixed solvent, is having N
2stir under (flow 0.15mL/min) protective condition, until solution clear.
(3) synthesis of CdSe quantum dot:
Se precursor solution and Cd precursor solution volume ratio are that 1:5 mixes, add the oleyl amine solution with Se precursor solution same volume, mix in 10mL syringe, control impeller speed, the reaction times making the polytetrafluoroethylene capillary through oil bath heating is 30s.Acetone washing dispersoid quantum dot solution, centrifugation 1 time, rotating speed is 9000r/min, colloidal precipitation is dispersed in toluene, obtains final product.
From Figure of description 1-4, the present embodiment gained quantum dot emission wavelength be 532nm, quantum yield reach 85% and halfwidth be 23.2nm.
Embodiment 2
(1) preparation of Se presoma:
Be dissolved in by 0.005mol selenium powder in 10mL trimethyl-phosphine (TOP), dispersion is stirred to the Se-TOP precursor solution forming evenly clarification;
(2) preparation of Cd presoma:
1-octadecylene mixes with 10: 1 with oleic acid volume, adds in Cadmium oxide 0.005mol to above-mentioned mixed solvent, is having N
2stir under (flow 0.15mL/min) protective condition, until solution clear.
(3) synthesis of CdSe quantum dot:
Se precursor solution and Cd precursor solution volume ratio are that 1:10 mixes, add the oleyl amine solution with Se precursor solution same volume, mix in 10mL syringe, control impeller speed, the reaction times making the polytetrafluoroethylene capillary through oil bath heating is 200s.Acetone washing dispersoid quantum dot solution, centrifugation 3 times, rotating speed is 9000r/min, colloidal precipitation is dispersed in toluene, obtains final product.
From Figure of description 6,7, the emission wavelength of the present embodiment gained quantum dot is 504nm, and quantum yield reaches 83%, and halfwidth is only 30nm.
Claims (10)
1. a method for the CdSe bare nucleus quantum dot that microfluid synthesis luminescent properties is controlled, comprising:
(1) be dissolved in solvent by Cadmium oxide, nitrogen protection, 300 DEG C of stirrings, obtain cadmium precursor solution;
(2) selenium is dissolved in solvent, stirring at room temperature, obtains selenium precursor solution;
(3) by cadmium precursor solution and selenium precursor solution mixing, pass in polytetrafluoroethylene capillary, by oil bath, reaction, then wash, centrifugal, dispersion, to obtain final product; Wherein the volume ratio of selenium precursor solution and cadmium precursor solution is 10:1 ~ 1:10.
2. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: in described step (1), solvent is the mixing solutions of 1-octadecylene and oleic acid.
3. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 2 is controlled, is characterized in that: the volume ratio of described 1-octadecylene and oleic acid is 1:2-1:10.
4. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: in described step (1), the concentration of cadmium precursor solution is 0.1-1.0mmol/mL.
5. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: in described step (2), solvent is tri octyl phosphine TOP.
6. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: in described step (2), the concentration of selenium precursor solution is 0.1-1.0mmol/mL.
7. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: in described step (3), temperature of reaction is 200-250 DEG C, and the reaction times is 2s-200s.
8. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, it is characterized in that: in described step (3), washing is for using washing with acetone 1-5 time, centrifugal rotational speed is 6000-9000r/min, centrifugation time 20-25min.
9. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, is characterized in that: described step is separated in (3): be dispersed in toluene or normal hexane.
10. the method for the CdSe bare nucleus quantum dot that a kind of microfluid synthesis luminescent properties according to claim 1 is controlled, it is characterized in that: the emission wavelength of described CdSe quantum dot is at 485nm ~ 610nm, quantum yield reaches 48% ~ 87%, and halfwidth is 17nm ~ 30nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI595924B (en) * | 2016-03-03 | 2017-08-21 | Method of synthesizing quantum dot material with microfluidic | |
| CN108905950A (en) * | 2018-06-29 | 2018-11-30 | 东华大学 | A kind of amorphous coated by titanium dioxide CdSe quantum dot and its preparation and application |
| CN109941977A (en) * | 2019-04-22 | 2019-06-28 | 中国科学院化学研究所 | A kind of synthetic method of CdSe quantum dots |
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| CN1562765A (en) * | 2004-03-23 | 2005-01-12 | 中国科学院上海技术物理研究所 | Method for preparing quantum point of cademium selenide |
| CN1986725A (en) * | 2006-12-14 | 2007-06-27 | 上海交通大学 | Preparing process of CdSe quantum dot |
| CN101585516A (en) * | 2009-06-15 | 2009-11-25 | 中国医药城泰州纳米生命医学研究院 | The preparation method of a kind of CdSe and CdSe-ZnSe core-shell quanta dots |
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Patent Citations (3)
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| CN1562765A (en) * | 2004-03-23 | 2005-01-12 | 中国科学院上海技术物理研究所 | Method for preparing quantum point of cademium selenide |
| CN1986725A (en) * | 2006-12-14 | 2007-06-27 | 上海交通大学 | Preparing process of CdSe quantum dot |
| CN101585516A (en) * | 2009-06-15 | 2009-11-25 | 中国医药城泰州纳米生命医学研究院 | The preparation method of a kind of CdSe and CdSe-ZnSe core-shell quanta dots |
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| QUANQIN DAI ET AL.: "Effect of ligands and growth temperature on the growth kinetics and crystal size of colloidal CdSe nanocrystals", 《MATERIALS LETTERS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI595924B (en) * | 2016-03-03 | 2017-08-21 | Method of synthesizing quantum dot material with microfluidic | |
| CN108905950A (en) * | 2018-06-29 | 2018-11-30 | 东华大学 | A kind of amorphous coated by titanium dioxide CdSe quantum dot and its preparation and application |
| CN109941977A (en) * | 2019-04-22 | 2019-06-28 | 中国科学院化学研究所 | A kind of synthetic method of CdSe quantum dots |
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Application publication date: 20150401 |