CN1789371A - Method for preparing II-VI type quantum - Google Patents
Method for preparing II-VI type quantum Download PDFInfo
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- CN1789371A CN1789371A CN 200510120547 CN200510120547A CN1789371A CN 1789371 A CN1789371 A CN 1789371A CN 200510120547 CN200510120547 CN 200510120547 CN 200510120547 A CN200510120547 A CN 200510120547A CN 1789371 A CN1789371 A CN 1789371A
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Abstract
The invention discloses the method for preparation of II-VI type quantum point and the method of carrying out water-solubility conversion. The method uses the metallic compound and nonmetallic substance powder as raw material, and prepares the quantum point of different grain diameters and compositions at the temperate condition. The method doesn't adopt the expensive and poisonous compounds, so operation is safe and easy, repeatability is good and cost is low. The products are equal and the monodispersity of the product is good, and the grain diameter can be controlled. The water-solubility quantum point possesses excellent fluorescence, water-solubility and stability. The product can be used for biology label, cell image formation, developing and other biology and medicine analysis fields.
Description
Technical field
The present invention relates to a kind of preparation method of II-VI type quantum dot, belong to analytical chemistry, nano science, surface chemistry, bioanalysis chemical field.
Background technology
Quantum dot (Quantum Dots, QDs) be often referred to radius less than or near the semiconductor nano crystal grain of exciton Bohr radius, they have unique fluorescence nano effect, for example it excites spectrum width and continuous distribution, emission spectrum is narrow and symmetrical, and emission wavelength can be regulated and control by changing particle diameter and composition, and fluorescence intensity is strong, bleaching speed is slow, highly sensitive, thereby has broad application prospects at aspects such as luminescent material, photochemical catalysis, photosensor, fluorescent probe marks.Especially the elementary composition quantum dot of IIB family and VIA family, abbreviate II-VI type quantum dot (as CdTe) as, owing to have special good visible and near infrared spectrum district fluorescent emission character, aspect biomedical fluorescent probe marker and the transmitter important value arranged.
Quanta point material synthesizes two big serial approach at present, a kind of is by the organometallics route, and the technology of similar synthetic CdSe quantum dot uses TOPO/HDA to make solvent, at high temperature the Se complex solution is injected the Cd precursor, obtain the quantum dot of different-grain diameter and fluorescent emission.In this field, Peng X.G. and his co-workers have a large amount of work.(Peng X G.J.Am.Chem.Soc.2001,123,183-184.) this synthetic route can obtain the good II-VI type of monodispersity quantum dot, comprises quantum dots such as CdSe, CdTe.But this method complicated operation need react under rare gas element, and employed solvent is inflammable, explosive, costliness and toxicity are stronger, is unfavorable for scale operation.
Another synthetic method is the protection by tensio-active agent in the aqueous solution; obtain CdTe quantum dot (Zhang Hao etc. by reaction under protection of inert gas; SCI 2003.1; 24; 178-180); this method also needs to use some special organic reagents, and the precursor of preparation NaHTe type has bigger danger equally.And the fluorescence quantum yield by the quantum dot that these class methods synthesized is lower.
The superior fluorescent characteristic of quantum dot itself makes it can be used as a kind of outstanding fluorescent marker and is applied to various fields, but by the quantum dot that the organic phase Pintsch process obtains all is oil-soluble, and all living things systems all are the polarity aqueous environment, so means and method by surface chemistry are modified the quantum dot surface, the success or not of the oil soluble quantum dot being carried out water-solubleization then is the bottleneck that the restriction quantum dot truly is widely used in the bioanalysis field.
Summary of the invention
For solving problems of the prior art, and realization is to water-solubleization of oil soluble quantum dot, the invention provides a kind of preparation method of II-VI type quantum dot, can safety by this method, efficiently, the synthetic quantum dot of cheap batch, and, become the nano material that can be applied to biological fluorescent labelling by water-soluble conversion.
Technical scheme provided by the invention is to prepare II-VI type quantum dot as follows:
(1) VI family element powders is added in the mixed solution of octadecylene (ODE) and phosphine compound, suitably heating makes it to dissolve fully, makes the solution that content is 0.01～0.05mol/L.
(2) II-B family metallic element compound is added in ODE and the longer chain fatty acid, be heated to 180～250 ℃, make the solution that metal ion content is 0.01～0.05mol/L.
(3) get VI family unit cellulose solution, join in 180～250 ℃ the II-B family metal ion solution, temperature generally can descend 20 ~ 30 ℃ after injection, react 5～300 seconds, and quencher is reacted in the impouring methyl alcohol, promptly makes quantum dot.
If with the quantum dot that makes, add tensio-active agent, under ultrasonic, the jolting or the effect of milling with quantum dot and surfactant-dispersed in water, the centrifugal unreacting substance of removing, solution is the quantum dot aqueous solution.
If with the quantum dot that makes, after cleaning, it is dispersed in N, in the dinethylformamide (DMF), add the organic acid reaction of band sulfydryl, centrifugal then, get supernatant, regulate the pH value to alkalescence with alkali, use tetrahydrofuran (THF) precipitation, the centrifugal supernatant liquid of removing, the gained precipitation is water-soluble quantum dot.
Wherein VI family element can be S, Se or Te, and II family metallic element can be Zn, Cd or Hg, and its compound can be oxide compound, acetate or oxalate.Used phosphine compound is TOP normally, also can use organic phosphine compounds such as TBP or TDPA partly or entirely to replace TOP as required.Longer chain fatty acid can be stearic acid or oleic acid, and its content is regulated between 0-50% as required.
Used tensio-active agent can be cetyl trimethylammonium bromide or sodium laurylsulfonate, and alkali can be the aqueous solution of six saturated methyne imines of the saturated NaOH of 0.01mol/l-or 0.01mol/l-.
In the present invention, can obtain the II-VI type quantum dot of different scale to the adjustment in charging capacity, temperature, reaction times.Because there is difference in the particle diameter of quantum dot, its fluorescent emission wavelength can increase and red shift with the diameter of quantum dot.
In the present invention, can obtain a series of different II-VI type quantum dots to the combination of different precursor elements, different according to forming, the fluorescent emission wave band difference of different quantum dots.
Adopt quantum dot synthetic method provided by the invention to compare with present employed method, method of the present invention has easy and simple to handle, safety feature.Compare with the certain methods that document is reported; present method adopts the ODE of safety non-toxic as solvent; use VI family's element simple substance and metal oxide or metal-salt to replace expensive and dangerous Organometallic precursor, be reflected in the air and can carry out, protection that need not rare gas element.The present invention is with low cost can easier to realize scale operation.
By water-solubleization of method realization II-VI type quantum dot provided by the invention, can obtain having the water-soluble quantum dot of the photoluminescent property of almost identical excellence with the oil soluble quantum dot.Product can make quantum dot and biomolecule action form quantum dot-labeled biomolecules (biologically-derivedization) selectively with going up different reactive groups or different electric charges.CTAB can make the water-soluble quantum dot surface positively charged, and SDS can make the water-soluble quantum dot surface electronegative.Also can design the water-soluble quantum dot that dissimilar surfactant-based functional moleculars obtains the different surfaces proterties as required.
Adopt method of the present invention to realize that water-solubleization of quantum dot has the following advantages: 1) You Yi photoluminescent property.2) simple and convenient, workable, the good reproducibility of modifying method, raw materials used safety are easy to get.Adopt with low cost and reagent that be easy to get just can obtain high-quality water-soluble quantum dot by simple method.Making processes is simple; 3) modification back quantum dot distribution of sizes is constant substantially; 4) this method prepares the product function of surface and can design specific functional group as required.In sum, the present invention is easy to operation, cost is low, good reproducibility, all can finish at general chemistry and Biochemistry Experiment chamber.
Description of drawings
Fig. 1: the process flow sheet of preparation CdTe quantum dot and the aqueous solution and water-soluble CdTe quantum dots.
Fig. 2: be the photo in kind of CdTe quantum dot.
Fig. 3: be the fluorescence photo of CdTe quantum dot.
Fig. 4: be the uv-absorbing and the fluorescent emission collection of illustrative plates of CdTe quantum dot.
Fig. 5: be the TEM photo of CdTe quantum dot.
Embodiment
Be example with CdTe below, in conjunction with specific embodiments the present invention further set forth that the flow process of following examples can be referring to Fig. 1.
The preparation of embodiment 1:CdTe quantum dot:
Get 13mg Te, 1ml ODE and 1ml TOP mix back uncovered suitable heating in air in little flask, and the dissolving back is stand-by fully.Note is made solution A.
Get 10ml ODE, 2ml oleic acid, 23mg CdO after mixing in round-bottomed flask, stirs, and is uncovered hot altogether down to 250 ℃ in air.Note is made solution B.
Solution A is injected solution B rapidly.With in a large amount of methyl alcohol in the rapid impouring large beaker of the reaction solution in the flask, reaction solution is cooled down rapidly behind the reaction 300s.Tell red quantum dot solution by separating funnel.Its photo is seen Fig. 2, and under the ultra violet lamp, its fluorescent emission is seen Fig. 3.
The preparation of embodiment 2:CdSe quantum dot:
Get 10mg Se, 1ml ODE and 1ml TOP mix back suitably heating in air in little flask, and the dissolving back is stand-by fully.Note is made solution A.
Get 10ml ODE, 0.3g stearic acid, 40mg Cd (Ac)
2, after in round-bottomed flask, mixing, stir, hot altogether to 220 ℃ in air.Note is made solution B.
Solution A is injected solution B rapidly.With in a large amount of methyl alcohol in the rapid impouring large beaker of the reaction solution in the flask, reaction solution is cooled down rapidly behind the reaction 15s.Tell the xanchromatic quantum dot solution by separating funnel.
Embodiment 3: the preparation of water-soluble quantum dot
Get quantum dot solution 0.3ml in the 2ml centrifuge tube, add 0.3ml methyl alcohol and 1.4ml acetone, by using the rotating speed centrifugation of 10000rpm behind the ultra-sonic dispersion, abandon and add methyl alcohol again behind the supernatant and acetone disperses, disperse repeatedly and centrifugal several obtains more purified quantum dot and precipitates.After precipitation is dispersed in 1ml DMF (N, dinethylformamide), add the 1ml thioglycolic acid, in shaking table, react 30min.5000rpm is centrifugal in the reaction back, gets supernatant in two 2ml centrifuge tubes, adds the NaOH solution of 0.5ml 1mol/L, adds tetrahydrofuran (THF) again to full, and 12000rpm is centrifugal, and the gained precipitation is water-soluble quantum dot.Be dissolvable in water in distilled water or the phosphate buffer solution.
Embodiment 4: the preparation of the quantum dot aqueous solution
Get quantum dot solution 0.3ml in the 2ml centrifuge tube, add 0.3ml methyl alcohol and 1.4ml acetone, 12000rpm centrifugation behind the ultra-sonic dispersion, in precipitation, add 10mg CTAB (cetyl trimethylammonium bromide) and fill it up with distilled water, ultra-sonic dispersion, the centrifugal unreacting substance of removing of 12000rpm, solution is the quantum dot aqueous solution.
The quantum dot Performance Detection:
Get quantum dot solution, on luminoscope, measure its absorption characteristic and fluorescent emission peak shape, as Fig. 4.Quantum dot should have the absorption curve as the feature of figure, comprises absorption band, quantum confinement peak etc.The fluorescence emission peak of quantum dot should be in quantum confinement peak long wave direction number nanometers, the narrow symmetry of peak shape.
Get quantum dot solution and drip on copper mesh, under infrared lamp, dry,, should be the mono-dispersed nano particle in transmission electron microscope (TEM) imaging down, uniform particle diameter, yardstick is below 10nm, as Fig. 5.
Claims (9)
1, a kind of preparation method of II-VI type quantum dot is characterized in that may further comprise the steps:
(1) VI family element powders is added in the mixed solution of octadecylene (ODE) and phosphine compound, suitably heating makes it to dissolve fully, makes the solution that content is 0.01～0.05mol/L.
(2) II-B family metallic element compound is added in ODE and the longer chain fatty acid, be heated to 180～250 ℃, make the solution that metal ion content is 0.01～0.05mol/L.
(3) get VI family unit cellulose solution, join in 180～250 ℃ the II-B family metal ion solution, temperature generally can descend 20 ~ 30 ℃ after injection, react 5～300 seconds, and quencher is reacted in the impouring methyl alcohol, promptly makes quantum dot.
2, according to the preparation method of the described II-VI type of claim 1 quantum dot, it is characterized in that: with the quantum dot that makes, add tensio-active agent, under ultrasonic, the jolting or the effect of milling with quantum dot and surfactant-dispersed in water, the centrifugal unreacting substance of removing, solution is the quantum dot aqueous solution.
3, according to the preparation method of the described II-VI type of claim 1 quantum dot, it is characterized in that:, after cleaning, it is dispersed in N the quantum dot that makes, in the dinethylformamide (DMF), add the organic acid reaction of band sulfydryl, centrifugal then, get supernatant, regulate the pH value to alkalescence with alkali, use tetrahydrofuran (THF) precipitation, the centrifugal supernatant liquid of removing, the gained precipitation is water-soluble quantum dot.
4, the preparation method of II-VI type quantum dot according to claim 1, it is characterized in that: VI family element is dissolved in ODE and obtains solution under the phosphine compound effect, phosphine compound is tri octyl phosphine (TOP) normally, also can use organic phosphine compounds such as TBP or TDPA partly or entirely to replace TOP as required.
5, the preparation method of II-VI type quantum dot according to claim 1 is characterized in that: VI family element can be S, Se or Te.
6, method according to claim 1 is characterized in that: II family metallic element can be Zn, Cd or Hg, and its compound can be oxide compound, acetate or oxalate.
7, method according to claim 1 is characterized in that: longer chain fatty acid can be stearic acid or oleic acid, and its content is regulated between 0-50% as required.
8, method according to claim 2 is characterized in that: tensio-active agent can be cetyl trimethylammonium bromide or sodium laurylsulfonate.
9, method according to claim 3 is characterized in that: alkali can be the aqueous solution of six saturated methyne imines of the saturated NaOH of 0.01mol/l-or 0.01mol/l-.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108481825A (en) * | 2018-05-22 | 2018-09-04 | 惠州市创亿达新材料有限公司 | Quantum dot optics feature board and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108481825A (en) * | 2018-05-22 | 2018-09-04 | 惠州市创亿达新材料有限公司 | Quantum dot optics feature board and preparation method thereof |
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