CN103320135A - Water-phase preparation method of CdZnTe quantum dots under acidic conditions - Google Patents
Water-phase preparation method of CdZnTe quantum dots under acidic conditions Download PDFInfo
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- CN103320135A CN103320135A CN2013102440302A CN201310244030A CN103320135A CN 103320135 A CN103320135 A CN 103320135A CN 2013102440302 A CN2013102440302 A CN 2013102440302A CN 201310244030 A CN201310244030 A CN 201310244030A CN 103320135 A CN103320135 A CN 103320135A
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Abstract
The invention relates to a water-phase preparation method of CdZnTe quantum dots, belonging to the technical field of composite nano microcrystal materials. The product of the invention is CdZnTe quantum dots. The preparation method comprises the following steps: reacting sodium borohydride (NaBH4) and tellurium powder (Te) to prepare sodium hydrogen telluride (NaHTe), and injecting the sodium hydrogen telluride into a zinc nitrate/cadmium nitrate/3-mercaptopropionic acid solution of which the pH value is regulated by sodium hydroxide so as to react, thereby obtaining a CdZnTe quantum dot solution. The product obtained by the method provided by the invention has the advantages of uniform dispersion, high stability, high quantum yield and less aggregation, and can be used in the fields of biological fluorescence labeling, drug isolation and some photoelectric devices.
Description
Technical field
The present invention relates to the aqueous phase preparation method of the CdZnTe quantum dot under a kind of acidic conditions, belong to composite Nano micro crystal material technical field.
Background technology
CdZnTe is a kind of group Ⅱ-Ⅵ compound semiconductor of photoelectric properties excellence, has uptake factor high, the advantages such as energy gap and solar spectrum are complementary, so that CdZnTe has broad application prospects in the solar cell preparation, want to realize the widespread use of CdZnTe in photoelectricity and biological field, must obtain the CdZnTe material of the high and stable luminescence of quantum yield.
The common technology of the synthetic CdZnTe nano material of water is under the effect of dispersion agent under the acidic conditions, allows Cd source, Zn source, Te source react under sour environment and generates the CdZnTe quantum dot solution.Compare with traditional oil phase preparation technology, aqueous process control simple to operate, easy, temperature of reaction are low, and the sample that obtains is water-soluble, and bio-compatibility is good.Compare with the synthetic CdZnTe quantum dot of water under the alkaline condition, the CdZnTe quantum dot that can synthesize the high Zn/Cd ratio that alkaline condition can't prepare under the acidic conditions (reduces the content of Cd in the CdZnTe quantum dot, thereby reduce the toxicity of quantum dot), and the quantum dot fluorescence emmission spectrum of preparation has the good characteristics such as halfwidth narrow (approximately 40nm), symmetry be good, and its quantum yield can reach 80%.Meanwhile, the CdZnTe quantum dot for preparing under the acidic conditions has good stability, the stability that the quantum dot that normal temperature was placed 150 days still can guarantee system.
Summary of the invention
The object of the present invention is to provide under a kind of acidic conditions water to prepare that fluorescence intensity is high, the method for the CdZnTe quantum dot of stable luminescence.
The present invention is the aqueous phase preparation method of CdZnTe quantum dot under a kind of acidic conditions, and its preparation process and step are as follows:
A. in the 100ml pear shape bottle, pass into nitrogen approximately behind the 30min, add successively 0.8mmolNaBH
4, 0.4mmol tellurium powder (Te) and 2ml deionized water; Then pear shape bottle placed ice bath (0 ℃), under nitrogen protection, react 8h, treat that black tellurium powder all disappears, generate the transparent settled solution I of lavender, i.e. NaHTe solution; Chemical equation is:
4NaBH
4?+?2Te?+7H
2O?——?2NaHTe?+?Na
2B
4O
7?+?14H
2↑
B. the 250ml there-necked flask passes into nitrogen with in the Bas Discharged, add successively cadmium nitrate, the zinc nitrate (mol ratio of change cadmium nitrate and zinc nitrate in the 100ml beaker, guarantee that its total amount is 3.2mmoL), 100ml deionized water and 400 μ L 3-thiohydracrylic acids, then with 1M NaOH pH value is adjusted to 6, above solution is injected there-necked flask, place 100 ℃ of oil baths to heat 0.5h there-necked flask, obtain the transparent settled solution II of pistac, i.e. Cd (NO
3)
2And Zn (NO
3)
2Mixing solutions;
C. with syringe the solution I is injected into rapidly in the solution II, continue to pass to nitrogen and keep 100 ℃ of oil baths, can obtain pistac CdZnTe quantum dot solution III behind the reaction 3h, keep reaction conditions that reaction is proceeded, different time can obtain the CdZnTe quantum dot of different glow colors and different luminous intensities.
The characteristics such as the CdZnTe quantum dot of the present invention preparation has good stability, reunites less, high luminous intensity make it demonstrate very large application prospect in fields such as biological fluorescent labelling and photoelectric materials.
Outstanding feature of the present invention is: (1) whole experimental system carries out under acidic conditions, carries out the constraint of the synthetic quantum dot of condition before breaking through, and prepares the CdZnTe quantum dot of high quantum production rate, high Zn/Cd ratio under solutions of weak acidity; (2) (100 ℃) are carried out in experiment under relatively low temperature, and experimental implementation is simple, and process is easily controlled.
Description of drawings
Fig. 1 the invention process makes X-ray diffraction (XRD) figure of sample;
Fig. 2 the invention process makes high power perspective electron microscope (HRTEM) photo of sample;
The UV, visible light that Fig. 3 the invention process makes sample absorbs (uv-vis) spectrum;
Fig. 4 the invention process makes photoluminescence (PL) spectrum of sample.
Embodiment
After now specific embodiments of the invention being described in
Embodiment
Preparation process and the step of the present embodiment are as follows:
A. in the 100ml pear shape bottle, pass into nitrogen approximately behind the 30min, add successively 0.8mmolNaBH
4, 0.4mmol tellurium powder (Te) and 2ml deionized water; Then pear shape bottle placed ice bath (0 ℃), under nitrogen protection, react 8h, treat that black tellurium powder all disappears, generate the transparent settled solution I of lavender, i.e. NaHTe solution;
B. the 250ml there-necked flask passes into nitrogen with in the Bas Discharged, add successively cadmium nitrate, the zinc nitrate (mol ratio of change cadmium nitrate and zinc nitrate in the 100ml beaker, guarantee that its total amount is 3.2mmoL), 100ml deionized water and 400 μ L 3-thiohydracrylic acids, then with 1M NaOH pH value is adjusted to 6, above solution is injected there-necked flask, place 100 ℃ of oil baths to heat 0.5h there-necked flask, obtain the transparent settled solution II of pistac, i.e. Cd (NO
3)
2And Zn (NO
3)
2Mixing solutions;
C. with syringe the solution I is injected into rapidly in the solution II, continue to pass to nitrogen and keep 100 ℃ of oil baths, can obtain pistac CdZnTe quantum dot solution III behind the reaction 3h, keep reaction conditions that reaction is proceeded, different time can obtain the CdZnTe quantum dot of different glow colors and different luminous intensities;
The present invention utilizes X-ray diffractometer, uv-absorbing spectrophotometer and fluorescent emission protractor that laboratory sample is carried out structure and fluorescence property analysis, and the ultrastructure of observing its nano microcrystalline by high resolution transmission electron microscope, its test result shows: as shown in Figure 1, there is obvious diffraction peak in the CdZnTe quantum dot under the different mol ratio about 24 ° and 40 °.Locate respectively corresponding cubic CdTe(111 of diffraction peak with 23.7 °, 39.3 °, 46.4 ° and 56.8 ° of standard P DF card comparisons), (220), (311) and (400) crystal face; 25.3 °, 29.2 °, 41.8 °, 51.8 ° and 66.7 ° locate diffraction peak respectively (111), (200), (220), (222) and (331) crystal faces of corresponding ZnTe; When Zn/Cd increases to 5:1 by 2:1, locate peak position for 24 ° and 40 ° and narrow down gradually and minor shifts occurs to the right; When Zn/Cd is 5:1, locate to occur faint diffraction peak for 51.8 ° and 66.7 °, (222) of corresponding ZnTe and (331) crystal face illustrate the increase along with Zn/Cd, the quantum dot component is moved to ZnTe by CdTe.Fig. 2 is that Zn/Cd is than high power transmission electron microscope (HRTEM) photo of obtaining sample for the CdZnTe quantum dot reaction 36h of 4:1.(a) figure can find out that the CdZnTe quantum dot is evenly distributed, good dispersity, and is comparatively clear without reunion and edge.(b) figure can find out approximately 5nm of CdZnTe lateral size of dots, can determine d=0.37nm by measuring spacing, composes as can be known (111) crystal face of its corresponding CdTe crystal of comparison standard pdf card by XRD among Fig. 1 again.Change the zinc cadmium ratio, make the CdZnTe quantum dot of different components, its ultra-violet absorption spectrum and fluorescence emission spectrum are as shown in Figure 3.Fig. 3 is the uv-visible absorption spectra of differential responses time CdZnTe quantum dot (Zn/Cd=4), prolongation with the reaction times, CdZnTe quantum dot ABSORPTION EDGE generation red shift, because the absorption spectrum that has quantum dot of quantum confined effect is not single absorption peak, by a plurality of absorption peak positions, so the quantum dots of different sizes can be excited by same monochromatic source simultaneously, produce different fluorescence excitations peak, its characteristic is better than the biomarker that a kind of wavelength only only excites a kind of common organic dye molecule.Fig. 4 is the fluorescence emission spectrum of differential responses time CdZnTe quantum dot (Zn/Cd=4), and along with the prolongation in reaction times, quantum dot is constantly grown up, its fluorescence emission peak generation red shift.Differential responses time (6h, 12h, 24h, 36h, 48h) corresponding emission peak halfwidth is respectively 49.5nm, 51.3nm, 54.9nm, 63.2nm, 63.8nm, prolongation along with the reaction times, the emission peak halfwidth constantly increases, and illustrates along with the particle quantum point grain diameter homogeneity of growing up weakens.Table 1 prolongs halfwidth (FWHM) and quantum yield (QY) for different Zn/Cd with digestion time than CdZnTe quantum dot variation obtains the sub-productive rate 78.97% of maximum amount when Zn/Cd is 1.
Claims (1)
1. the aqueous phase preparation method of CdZnTe quantum dot under the acidic conditions is characterized in that having following preparation process and step:
A. in the 100ml pear shape bottle, pass into nitrogen approximately behind the 30min, add successively 0.8mmolNaBH
4, 0.4mmol tellurium powder (Te) and 2ml deionized water; Then pear shape bottle placed ice bath (0 ℃), under nitrogen protection, react 8h, treat that black tellurium powder all disappears, generate the transparent settled solution I of lavender, i.e. NaHTe solution;
B. in the 250ml there-necked flask, add successively 1.6mmol cadmium nitrate, 1.6mmol zinc nitrate, 100ml deionized water and 400 μ L 3-thiohydracrylic acids, pass into the oxygen in the nitrogen removal solution, then regulate PH to 6.0 with 1M NaOH, place 100 ℃ of oil baths to heat 1h three-necked flask, obtain water white transparency settled solution II, i.e. Cd (NO
3)
2With Zn (NO
3)
2Mixing solutions;
C. with syringe the solution I is injected into rapidly in the solution II, continues to pass to nitrogen and keep 100 ℃ of oil baths, obtain the CdZnTe quantum dot solution of the transparent clarification of pistac behind the reaction 3h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555333A (en) * | 2013-10-10 | 2014-02-05 | 上海大学 | Water phase preparation method for ZnTe-coated CdZnTe quantum dot |
| CN105524616A (en) * | 2015-11-25 | 2016-04-27 | 上海大学 | Aqueous phase preparation method for CdZnTe: Eu quantum dot |
| CN108998031A (en) * | 2018-10-18 | 2018-12-14 | 中国人民解放军陆军炮兵防空兵学院 | A method of preparing cadmium-zinc-teiluride quantum dot |
-
2013
- 2013-06-19 CN CN201310244030.2A patent/CN103320135B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| HUA HE ET AL.: "Designed Short RGD Peptides for One-Pot Aqueous Synthesis of Integrin-Binding CdTe and CdZnTe Quantum Dots", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555333A (en) * | 2013-10-10 | 2014-02-05 | 上海大学 | Water phase preparation method for ZnTe-coated CdZnTe quantum dot |
| CN105524616A (en) * | 2015-11-25 | 2016-04-27 | 上海大学 | Aqueous phase preparation method for CdZnTe: Eu quantum dot |
| CN108998031A (en) * | 2018-10-18 | 2018-12-14 | 中国人民解放军陆军炮兵防空兵学院 | A method of preparing cadmium-zinc-teiluride quantum dot |
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