CN101570322A - Method for synthesizing blue thioglycolic acid CdTe quantum dot by alcohol-water system - Google Patents
Method for synthesizing blue thioglycolic acid CdTe quantum dot by alcohol-water system Download PDFInfo
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- CN101570322A CN101570322A CNA2009100595533A CN200910059553A CN101570322A CN 101570322 A CN101570322 A CN 101570322A CN A2009100595533 A CNA2009100595533 A CN A2009100595533A CN 200910059553 A CN200910059553 A CN 200910059553A CN 101570322 A CN101570322 A CN 101570322A
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Abstract
The invention relates to a method for preparing blue CdTe quantum dot by an alcohol-water system. The method comprises the steps of using a hydrolytic cadmium salt as raw material, using the mercapto-carboxylate acid as a coordination agent, and synthesizing the blue CdTe quantum dot with the quantum yield of 12% in the alcohol-water system in certain proportion. The operation of the method is simple and feasible, the conditions are moderate, the cost is low, and the toxicity is small. The method can be conveniently used for commercial production on a large scale.
Description
Technical field
The present invention relates to a kind of preparation method of blue CdTe quantum dot.
Background technology
Quantum dot (Quantum Dots) is a based semiconductor nano material and since its particle diameter less than or near the exciton Bohr radius, its behavior has Quantum Properties.Electronics in the quantum dot and hole be by quantum confinement, can be with continuously to become discrete energy levels structure with molecular characterization, when electronics when conduction band transits to valence band, can launch the light of different wave length.Owing to be a kind of inorganic nano material,, have tunable wave length, exciting light spectrum width, optical stability height and the high advantage of quantum yield than traditional organic fluorescence reagent.Closely during the last ten years, all obtained good progress at aspects such as cell imaging, tumor marker, microorganism detection, photodiode (LED) and solar cells, and demonstrated wide application prospect in these fields.
At present, studying many is II-VI type quantum dot, as CdS, CdSe, CdTe, ZnS, ZnSe etc.Wherein, developed the synthetic high-quality CdTe of the whole bag of tricks.Laugh at firm group as Peng and reported (J.Am.Chem.Soc.2001,123 (1), 183-184.) under the condition of anhydrous and oxygen-free, with trioctylphosphine oxide (TOPO), tetradecene phosphonic acids (TDPA), hexyl phosphonic acids (HPA) is part, under 300 ℃, the CdO dissolving forms the Cd part, adds a certain amount of Te powder that is dissolved in positive tri octyl phosphine (TOP) then, and it is nanocrystalline to form CdTe.The synthetic quantum dot of organo-metallic decomposition method needs deleterious metal ligand and pyroreaction, and the quantum dot that is synthesized surface is hydrophobic organic carbochain, and is water-soluble and biocompatibility is all very poor, needs through could further using after the ligand exchange.And directly be stablizer with the sulfhydryl compound, at the directly synthetic CdTe quantum dot of aqueous phase, though the nanocrystal growth that does not have the organo-metallic decomposition method to synthesize is improved and size distribution is even, but it is simple to have method, do not need deleterious chemical reagent and hot environment, product has more friendly biocompatibility, can directly use biomarker, is a kind of synthetic method of green.As being part, can synthesize the green CdTe quantum dot at aqueous phase system with Thiovanic acid; With the gsh is stablizer, can synthesize red quantum dot.Till now, the emmission spectrum of the CdTe quantum dot that is synthesized in the aqueous phase system is all in 540 nanometers～650 nanometers, also not about directly synthesize the report of the blue quantum dot of CdTe in aqueous phase system.
Is a kind of important applied field of semiconductor nano with quantum dot for material preparation LED, compares with polymer LED, has that preparation process is simple, cost is low, photochromic purity advantages of higher.Because blue quantum dot be difficult to obtain, report that now more is green, yellow, orange and red LED.As everyone knows, blueness is one of three primary colors of color, and the preparation of blue led is extremely important in fields such as LED display and LED illuminations.With the extensive synthesizing blue quantum dot of the method for simple and feasible is an important prerequisite condition of preparation blue led.
Summary of the invention
The invention provides novel method a kind of green, that can synthesize the blue CdTe quantum dot of high quantum production rate on a large scale, remedied can not synthesizing blue CdTe quantum dot at aqueous phase system defective.
The method of alcohol-water system synthesizing blue CdTe quantum dot provided by the invention in turn includes the following steps:
(1) preparation of Te precursor solution.This solution is by analytically pure Te powder and NaBH
4Or KBH
4In pure water, reacted 30 minutes under the nitrogen protection, get the fresh NaHTe or the KHTe aqueous solution;
(2) a certain proportion of Cd that contains of configuration
2+Alcohol-water mixed solution.Alcohol in a certain proportion of pure water mixed solution can be: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, just oneself, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, n-undecane alcohol, n-dodecane alcohol, n-tetradecanol, cetyl alcohol (hexadecanol), Octadecane alcohol (stearyl alcohol), NSC 62789 alcohol (n-Eicosanol), positive behenyl alcohol, policosanol, 2-propyl alcohol, 2-butanols, 2-hexanol, hexalin, uncle's fourth, trityl alcohol or glycerol.The certain water miscible cadmium salt of weighing comprises Cadmium chloride fine powder, cadmium bromide, cadmium nitrate or cadmium acetate etc., Cd in the final solution
2+Concentration is 1mmol/L;
(3) in solution, add a certain amount of mercaptocarboxylic acids.Mercaptocarboxylic acids comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate or sulfydryl butyrates.Under magnetic agitation, be 9.0～11.0 with the pH of NaOH regulator solution;
(4) add the Te source.After 30 minutes, add the NaHTe or the KHTe aqueous solution of a certain amount of prepared fresh with inert gas deaeration, under protection of inert gas, reflux 5～12 hours, product is the CdTe quantum dot solution that blue Thiovanic acid is a stablizer.
Synthetic method feature of the present invention is that the solution of using in synthesizing is a certain proportion of alcohol-water system, and coordination agent is a mercaptocarboxylic acids, and product feature is the CdTe of emission wavelength in 400 nanometers～440 nanometers, and its quantum yield can reach 12%.This method is green preparation, can amplify syntheticly on a large scale, can be used for the preparation of various marks and blue led.
Description of drawings
Fig. 1 is the spectral signature of the typical blue CdTe quantum dot of the present invention's preparation;
Fig. 2 is the in kind picture of blue CdTe quantum dot under visible light and uv irradiating of the present invention's preparation;
Fig. 3 is the high-resolution transmission electron microscope picture of the blue CdTe quantum dot of the present invention's preparation.
Embodiment
Embodiment 1
1) in 50mL exsiccant three cervical vertebra shape flasks, adds analytically pure Te powder of 30mg and 40mg NaBH
4, adding the secondary water of 15mL deoxygenation then, purplish red solution is produced in the protection of inert gas reaction in 60 ℃ water-bath, is the NaHTe solution of prepared fresh;
2) in 250mL three neck round-bottomed flasks, add 50mL and contain 1mmol/L Cd
2+The 60% alcoholic acid aqueous solution, under magnetic agitation, add 20 μ L Thiovanic acids, stirs after 5 minutes, be 9.5 with the NaOH conditioned reaction pH of 1mmol/L, feeding rare gas element (argon gas or nitrogen) deoxygenation 30 minutes;
3) the NaHTe solution of getting 100 μ L prepared fresh rapidly adds 2) solution in, continued magnetic agitation 10 minutes;
4) round-bottomed flask is moved into heating jacket, and install condensing works, under rare gas element (argon gas or nitrogen) protection, reflux 5 hours promptly gets clear soln.Get this solution and characterize, be blue CdTe quantum dot.
Embodiment 2
1) in 50mL exsiccant three cervical vertebra shape flasks, adds analytically pure Te powder of 30mg and 40mg KBH4, the secondary water that adds the 15mL deoxygenation then, the protection of inert gas reaction is 20 minutes in 70 ℃ water-bath, gets colourless transparent liquid, is the KHTe solution of prepared fresh;
2) in 250mL three neck round-bottomed flasks, add 50mL and contain 1mmol/L Cd
2+The aqueous solution of 60% n-propyl alcohol, under magnetic agitation, add 20 μ L Thiovanic acids, stirs after 5 minutes, be 9.5 with the NaOH conditioned reaction pH of 1mmol/L, feeding rare gas element (argon gas or nitrogen) deoxygenation 30 minutes;
3) the KHTe aqueous solution of getting 100 μ L prepared fresh rapidly adds 2) solution in, continued magnetic agitation 10 minutes;
4) round-bottomed flask is moved into heating jacket, and install condensing works, under rare gas element (argon gas or nitrogen) protection, reflux 6 hours promptly gets clear soln.Get this solution and characterize, be blue CdTe quantum dot.
Embodiment 3
1) add analytically pure Te powder of 50mg and 70mgNaBH4 in 50mL exsiccant three cervical vertebra shape flasks, add the secondary water of 20mL deoxygenation then, purplish red solution is produced in the protection of inert gas reaction in 80 ℃ water-bath, is the NaHTe solution of prepared fresh;
2) in 250mL three neck round-bottomed flasks, add 50mL and contain 1mmol/L Cd
2+The 70% alcoholic acid aqueous solution, under magnetic agitation, add 20 μ L thiohydracrylic acids, stirs after 5 minutes, be 9.5 with the NaOH conditioned reaction pH of 1mmol/L, feeding rare gas element (argon gas or nitrogen) deoxygenation 30 minutes;
3) the NaHTe aqueous solution of getting 80 μ L prepared fresh rapidly adds 2) solution in, continued magnetic agitation 10 minutes;
4) round-bottomed flask is moved into heating jacket, and install condensing works, under rare gas element (argon gas or nitrogen) protection, reflux 12 hours promptly gets clear soln.Get this solution and characterize, be blue CdTe quantum dot.
Claims (5)
1. a Thiovanic acid is the preparation method of the blue quantum dot CdTe of stablizer quantum dot, it is characterized in that adopting following step:
(a) in the exsiccant flask, add Te powder and NaBH
4Or KBH
4, adding a certain amount of deionized water, reaction is 30 minutes under nitrogen protection, gets the fresh NaHTe or the KHTe aqueous solution;
(b) adding is dissolved with certain density Cd in three-necked flask
2+A certain proportion of alcohol solution (alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.) 50mL, under magnetic agitation, add mercaptocarboxylic acids, regulate pH to 9.0～11.0 with NaOH then, feed argon gas, stirred 30 minutes, remove the dissolved oxygen of the inside;
(c) NaHTe or the KHTe solution of a certain amount of prepared fresh of adding in above-mentioned solution, under argon shield, reflux 5～12 hours, blue Thiovanic acid promptly is the CdTe quantum dot of stablizer;
(d) get this solution and characterize with spectrophotofluorometer, excite down in excitation light source 310 nanometers, the fluorescence maximum emission wavelength is in 400 nanometers～440 nanometers.
2. synthetic method according to claim 1 is characterized in that used cadmium salt comprises all water-soluble cadmium salts, as Cadmium chloride fine powder, cadmium bromide, cadmium nitrate, cadmium acetate etc.
3. synthetic method according to claim 1 is characterized in that the alcohol in the pure water mixed solution of any ratio comprises: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, just oneself, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, n-undecane alcohol, n-dodecane alcohol, n-tetradecanol, cetyl alcohol (hexadecanol), Octadecane alcohol (stearyl alcohol), NSC 62789 alcohol (n-Eicosanol), positive behenyl alcohol, policosanol, 2-propyl alcohol, 2-butanols, 2-hexanol, hexalin, uncle's fourth, trityl alcohol, glycerol.
4. synthetic method according to claim 1 is characterized in that used mercaptan carboxylic acid comprises: Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, sulfydryl butyrates.
5. synthetic method according to claim 1, it is characterized in that synthesize the emission wavelength of CdTe quantum dot in 400 nanometers～440 nanometer range.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094253A (en) * | 2010-12-23 | 2011-06-15 | 黑龙江大学 | Preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers |
| CN102877149A (en) * | 2012-10-25 | 2013-01-16 | 黑龙江东方学院 | In-situ preparation method for cadmium telluride/polyvinyl alcohol fluorescent fiber |
| CN103979504A (en) * | 2014-05-07 | 2014-08-13 | 东南大学 | Preparation method of electropositive water-soluble cadmium telluride quantum dots |
| CN104927867A (en) * | 2015-06-03 | 2015-09-23 | 四川农业大学 | Ratiometric fluorescent probe for bivalent copper ions, as well as preparation method and application of ratiometric fluorescent probe |
| CN106867540A (en) * | 2017-03-27 | 2017-06-20 | 天津工业大学 | The quick preparation of fluorescence CdTe quantum dot high |
| CN110002413A (en) * | 2019-03-12 | 2019-07-12 | 浙江大学 | A kind of CdTe quantum multilevel structure and preparation method thereof |
-
2009
- 2009-06-10 CN CNA2009100595533A patent/CN101570322A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094253A (en) * | 2010-12-23 | 2011-06-15 | 黑龙江大学 | Preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers |
| CN102094253B (en) * | 2010-12-23 | 2012-10-24 | 黑龙江大学 | Preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers |
| CN102877149A (en) * | 2012-10-25 | 2013-01-16 | 黑龙江东方学院 | In-situ preparation method for cadmium telluride/polyvinyl alcohol fluorescent fiber |
| CN103979504A (en) * | 2014-05-07 | 2014-08-13 | 东南大学 | Preparation method of electropositive water-soluble cadmium telluride quantum dots |
| CN103979504B (en) * | 2014-05-07 | 2015-12-30 | 东南大学 | A kind of preparation method of positive polarity water soluble cadmium telluride quantum point |
| CN104927867A (en) * | 2015-06-03 | 2015-09-23 | 四川农业大学 | Ratiometric fluorescent probe for bivalent copper ions, as well as preparation method and application of ratiometric fluorescent probe |
| CN106867540A (en) * | 2017-03-27 | 2017-06-20 | 天津工业大学 | The quick preparation of fluorescence CdTe quantum dot high |
| CN110002413A (en) * | 2019-03-12 | 2019-07-12 | 浙江大学 | A kind of CdTe quantum multilevel structure and preparation method thereof |
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