CN1306004C - Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point - Google Patents
Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point Download PDFInfo
- Publication number
- CN1306004C CN1306004C CNB2005100255073A CN200510025507A CN1306004C CN 1306004 C CN1306004 C CN 1306004C CN B2005100255073 A CNB2005100255073 A CN B2005100255073A CN 200510025507 A CN200510025507 A CN 200510025507A CN 1306004 C CN1306004 C CN 1306004C
- Authority
- CN
- China
- Prior art keywords
- cadmium
- quantum dot
- solution
- cdse
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention belongs to the technical field of nanometer materials and bioanalysis detection, which particularly relates to a preparation method of water soluble nucleus / shell type CdSe/CdS quantum dots. Cadmium chloride or cadmium perchlorate and other inorganic substances are used as raw materials, and water soluble nucleus / shell type CdSe/CdS quantum dots are prepared under the mild conditions. The method is completely carried out in a water phase and has the advantages of safe and convenient operation, favorable repeatability and small toxicity; the obtain products have the advantages of favorable monodispersion, good stability and water solubility; compared with a single CdSe quantum dot, the fluorescence property and the quantum yield of the products are greatly improved; the products can be widely used as fluorescent markers for biological detection and analysis.
Description
Technical field
The invention belongs to nano material and bioanalysis detection technique field, be specifically related to the preparation method of a kind of water-soluble CdSe/CdS core/shell type quantum dot.
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.When the diameter of quantum dot during less than Bohr's diameter of its electronics, quantum dot has quantum size effect to electronics, and its emission wavelength is relevant with nanocrystalline size.Compare with the organic fluorescence molecule, the fluorescence quantum crystalline substance has the following advantages: 1, its excitation spectrum almost is a successive absorbing more than the threshold value, is beneficial to multi-wavelength excitation; 2, high-strength fluorescent emission, the spectrum peak is narrow, the peak shape symmetry; 3, emission wavelength red shift regularly along with the increase of particle diameter only needs to change particle diameter and can obtain multicolor luminous; 4, the stability of photoluminescence of quantum dot is good, is difficult for by photolysis and bleaching.Therefore, quantum dot is more and more paid close attention to by scientist as biological marker of new generation.
The biological mark requires to use water miscible nanoparticle, the synthetic quantum point operation of water is easy, repeatability is high, cost is low, surface charge and surface properties are controlled, be easy to introduce various molecule of functional group, so the synthetic quantum dot of water becomes the focus of current research.On the other hand, there are a large amount of non-radiative recombination centers in the easy oxidation of single quantum dot, the instability for preparing, and surface usually, and these all cause, and quantum dot light emitting efficient is low, the fluorescence spectrum peak width at half height is too wide.Can be in single quantum dot surface epitaxy one deck lattice constant match, the wideer inorganic materials in energy gap, thus the lip-deep a large amount of defectives of quantum dot eliminated to a certain extent, improve the luminescent properties of quantum dot.At present the report for preparing CdSe/CdS core/shell type quantum dot about organic phase had a lot (J.Am.Chem.Soc so far since 1997,1997,119:7019-7029, J.Am.Chem.Soc, 2003,125:12567-12575, J.Am.Chem.Soc, 2003,125:3901-3909, Chem Mater, 2003,15:3125-3133, Appl Phy Lett, 2004,84:2223-2225), but the report of water-soluble CdSe/CdS core/shell type quantum dot seldom, and this has limited to a great extent CdSe/CdS core/shell type quantum dot is directly used in biomarker.
Summary of the invention
The objective of the invention is at problem recited above, the preparation method of a kind of operational safety, simple and easy to do water-soluble CdSe/CdS core/shell type quantum dot is provided.
The preparation method of water-soluble CdSe provided by the invention/CdS core/shell type quantum dot, concrete steps are as follows:
1, (a) is dissolved in Na with selenium powder
2SO
3In the solution, prepare Na as selenium source
2SeSO
3Solution; Be dissolved in the ultrapure water with sulfhydryl compound with as the cadmium salt in cadmium source, prepare cadmium-sulfydryl complex solution; (b), prepare cadmium-sulphur-sulfydryl complex solution with sulfhydryl compound, be dissolved in the ultrapure water as the cadmium salt and the sulphur source in cadmium source;
2, cadmium-sulfydryl complex solution is put into reactor A, logical nitrogen makes reactor A be full of rare gas element under pH value 7～11 conditions, stirs down at 80～100 ℃, injects Na
2SeSO
3Solution obtains containing the thick solution of CdSe quantum dot, is cooled to 15～50 ℃;
3, cadmium-sulphur-sulfydryl complex solution is put into reactor B, logical nitrogen makes reactor B be full of rare gas element under pH value 7～11 conditions, under 90～100 ℃ of conditions, stir, injection contains the thick solution of CdSe quantum dot, refluxed 15～120 hours under 80～100 ℃ of conditions, can obtain required CdSe/CdS core/shell type quantum dot.Obtaining product is the yellow-green colour clear solution of hyperfluorescence.
Above in the described step 1 (a): raw material cadmium source, sulfhydryl compound, selenium source are Cd in molar ratio
2+: sulfhydryl compound: SeSO
3 2-=1: (1.5～5): (0.3～0.7).
Above in the described step 1 (b), raw material cadmium source, sulfhydryl compound, sulphur source are Cd in molar ratio
2+: sulfhydryl compound: S
2-=1: (1.5～5): (0.3～0.7).
Cadmium of the present invention source is Cadmium chloride fine powder or cadmium perchlorate or their hydrate, and cadmium salt concentration is 10
-5～10
-2The M scope; Described sulfhydryl compound is Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol etc.
The present invention as raw material, has prepared the water-soluble CdSe/CdS quantum dot of core/shell type with inorganicss such as Cadmium chloride fine powder or cadmium perchlorates under the condition of gentleness.Present method is finished at aqueous phase, operational safety, easy, and good reproducibility, toxicity are less.Adopt the present invention prepare gained core/shell type the water-soluble quantum dot homogeneous and good monodispersity is arranged, CdSe quantum dot before the relative coating with quantum yield of photoluminescent property improves a lot, good stability, because it is water-soluble that it has, and can be used as fluorescent marker and be widely used in biological detection and analysis.
Description of drawings
Fig. 1 is the ultraviolet-fluorescence spectrum of the CdSe/CdS core/shell type quantum dot for preparing with the present invention;
Fig. 2 is the TEM and the HRTEM result of the CdSe/CdS core/shell type quantum dot for preparing with the present invention;
Embodiment
In order to understand content of the present invention better, further specify the present invention below by embodiment and legend.
The preparation of CdSe/CdS core/shell type quantum dot is divided into two portions: (a) preparation of the single quantum dot of CdSe; (b) be nuclear epitaxy CdS with CdSe, prepare CdSe/CdS core/shell type quantum dot.
Embodiment 1
1, gets 0.31g Na
2SO
3With 4.10mg Se powder, place single neck flask with 5ml, add the 4ml pure water, be heated to 90 ℃ under the nitrogen protection, reacted 20 hours, obtain Na
2SeSO
3Solution.
2, with 10ml 2.4 * 10
-3Mol/LMPA+1.0 * 10
-3Mol/L CdCl
2Mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 100 ℃, injects 0.3ml Na under the vigorous stirring
2SeSO
3Solution.Stop heating, be cooled to room temperature gradually, obtain the CdSeNCs clear solution.This solution excites at 365nm and issues orange-colored light.
3, preparation 100ml 4.8 * 10
-3Mol/L MPA+1.0 * 10
-3Mol/L CdCl
2+ 0.8 * 10
-3Mol/L Na
2The S mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 100 ℃, injects the 10ml CdSeNCs solution for preparing under the vigorous stirring, and 100 ℃ keep refluxing 24 hours down, obtain CdSe/CdS core/shell type quantum dot.
Embodiment 2
1, gets 1.5g Na
2SO
3With 21.5mg Se powder, place single neck flask with 25ml, add the 15ml pure water, be heated to 100 ℃ under the nitrogen protection, reacted 35 hours, obtain Na
2SeSO
3Solution.
2, with 5ml 2.5 * 10
-2Mol/L MPA+1.0 * 10
-2Mol/L CdCl
2Mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 90 ℃, injects 1ml Na under the vigorous stirring
2SeSO
3Solution.Stop heating, be cooled to 15 ℃ gradually, obtain the CdSeNCs clear solution.
3, preparation 100ml 1.0 * 10
-2Mol/L MPA+6.0 * 10
-3Mol/L CdCl
2+ 2.5 * 10
-3Mol/L Na
2The S mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 100 ℃, injects the 1.5ml CdSeNCs solution for preparing under the vigorous stirring, and 100 ℃ keep refluxing 50 hours down, obtain CdSe/CdS core/shell type quantum dot.
Embodiment 3
1, gets 0.60g Na
2SO
3With 10.5mg Se powder, place single neck flask with 100ml, add the 50ml pure water, be heated to 80 ℃ under the nitrogen protection, reacted 24 hours, obtain Na
2SeSO
3Solution.
2, with 15ml 2.8 * 10
-3Mol/LMPA+1.5 * 10
-3Mol/LCdCl
2Mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 90 ℃, injects 5ml Na under the vigorous stirring
2SeSO
3Solution.Stop heating, be cooled to 30 ℃ gradually, obtain the CdSeNCs clear solution.
3, preparation 100ml 6.0 * 10
-3Mol/L MPA+1.5 * 10
-3Mol/L CdCl
2+ 1.0 * 10
-3Mol/L Na
2The S mixing solutions, letting nitrogen in and deoxidizing 30 minutes is warming up to 110 ℃, injects the 15ml CdSeNCs solution for preparing under the vigorous stirring, and 100 ℃ keep refluxing 48 hours down, obtain CdSe/CdS core/shell type quantum dot.
By the method for the invention, can prepare the water-soluble core/shell type quantum point of other type-stable agent.
Claims (4)
1, the preparation method of a kind of water-soluble CdSe/CdS core/shell type quantum dot is characterized in that concrete steps are as follows:
(1) a, selenium powder is dissolved in Na
2SO
3In the solution, prepare Na as selenium source
2SeSO
3Solution; Be dissolved in the ultrapure water with sulfhydryl compound with as the cadmium salt in cadmium source, prepare cadmium-sulfydryl complex solution; B, sulfhydryl compound, cadmium salt and sulphur source are dissolved in the ultrapure water, prepare cadmium-sulphur-sulfydryl complex solution;
(2) cadmium-sulfydryl complex solution is put into reactor A, logical nitrogen makes reactor A be full of rare gas element under pH value 7～11 conditions, stirs under 80～100 ℃ of conditions, injects Na
2SeSO
3Solution obtains containing the thick solution of CdSe quantum dot, is cooled to 15～50 ℃;
(3) cadmium-sulphur-sulfydryl complex solution is put into reactor B, logical nitrogen makes reactor B be full of rare gas element under pH value 7～11 conditions, under 90～100 ℃ of conditions, stir, injection contains the thick solution of CdSe quantum dot, refluxed 15～120 hours under 80～100 ℃ of conditions, obtain required CdSe/CdS core/shell type quantum dot product;
Wherein, said sulfhydryl compound is Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine or Gelucystine.
2, preparation method according to claim 1 is characterized in that among a of step (1): raw material cadmium source, sulfhydryl compound, selenium source are Cd in molar ratio
2+: sulfhydryl compound: SeSO
3 2-=1: (1.5～5): (0.3～0.7).
3, preparation method according to claim 1 is characterized in that among the b of step (1): cadmium source, sulfhydryl compound, sulphur source are Cd in molar ratio
2+: sulfhydryl compound: S
2-=1: (1.5～5): (0.3～0.7).
4, according to claim 2 or 3 described preparation methods, it is characterized in that: said cadmium source is Cadmium chloride fine powder or cadmium perchlorate or their hydrate, and cadmium salt concentration is 10
-5～10
-2The M scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100255073A CN1306004C (en) | 2005-04-28 | 2005-04-28 | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100255073A CN1306004C (en) | 2005-04-28 | 2005-04-28 | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1693208A CN1693208A (en) | 2005-11-09 |
| CN1306004C true CN1306004C (en) | 2007-03-21 |
Family
ID=35352355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100255073A Expired - Fee Related CN1306004C (en) | 2005-04-28 | 2005-04-28 | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1306004C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413938C (en) * | 2006-07-07 | 2008-08-27 | 中国科学技术大学 | Au/CdSe heterostructure quantum point and its preparation method |
| CN101260294B (en) * | 2008-03-06 | 2010-06-02 | 河南大学 | Method for preparing nano-crystal with core-shell structure |
| CN102071453B (en) * | 2010-12-14 | 2012-05-02 | 吉林大学 | Method for preparing high-quality aqueous phase semiconductor nanocrystals by one pot method at room temperature |
| CN105154086A (en) * | 2015-09-29 | 2015-12-16 | 复旦大学 | Method for preparing CdSe/CdS nuclear shell semiconductor quantum dots at normal temperature |
| CN105586028B (en) * | 2016-03-10 | 2017-09-22 | 福州大学 | A kind of preparation method of CdSe@CdS core core-shell structure quantum dots |
| CN105885847B (en) * | 2016-04-08 | 2018-11-30 | 武汉理工大学 | A kind of cadmium sulfoselenide solid solution quantum dot and preparation method thereof and Photocatalyzed Hydrogen Production application |
| CN107219684A (en) * | 2017-07-26 | 2017-09-29 | 南通创亿达新材料股份有限公司 | A kind of quantum feature board and preparation method thereof |
| CN109825299A (en) * | 2019-01-22 | 2019-05-31 | 五邑大学 | A kind of preparation method of the CdSe quantum dot lyosol based on CdS modification |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322901B1 (en) * | 1997-11-13 | 2001-11-27 | Massachusetts Institute Of Technology | Highly luminescent color-selective nano-crystalline materials |
| CN1342515A (en) * | 2000-09-13 | 2002-04-03 | 湖南大学 | Nm-class core-and-shell particles |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
| WO2004066361A2 (en) * | 2003-01-22 | 2004-08-05 | The Board Of Trustees Of The University Of Arkansas | Monodisperse core/shell and other complex structured nanocrystals and methods of preparing the same |
| US6872249B2 (en) * | 2000-10-04 | 2005-03-29 | The Board Of Trustees Of The University Of Arkansas | Synthesis of colloidal nanocrystals |
-
2005
- 2005-04-28 CN CNB2005100255073A patent/CN1306004C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322901B1 (en) * | 1997-11-13 | 2001-11-27 | Massachusetts Institute Of Technology | Highly luminescent color-selective nano-crystalline materials |
| CN1342515A (en) * | 2000-09-13 | 2002-04-03 | 湖南大学 | Nm-class core-and-shell particles |
| US6872249B2 (en) * | 2000-10-04 | 2005-03-29 | The Board Of Trustees Of The University Of Arkansas | Synthesis of colloidal nanocrystals |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
| WO2004066361A2 (en) * | 2003-01-22 | 2004-08-05 | The Board Of Trustees Of The University Of Arkansas | Monodisperse core/shell and other complex structured nanocrystals and methods of preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1693208A (en) | 2005-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1306004C (en) | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point | |
| Mahmoud et al. | Synthesis, characterization and luminescence properties of thiol-capped CdSe quantum dots at different processing conditions | |
| Shen et al. | High quality synthesis of monodisperse zinc-blende CdSe and CdSe/ZnS nanocrystals with a phosphine-free method | |
| Wang et al. | Hydrothermal synthesis of high-quality type-II CdTe/CdSe quantum dots with near-infrared fluorescence | |
| CN1306003C (en) | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point by microwave radiation reaction | |
| CN101077976A (en) | Method of preparing CdTe/CdS/ZnS core-shell-core structure quantum points | |
| Comparelli et al. | Improved optical properties of CdS quantum dots by ligand exchange | |
| Lü et al. | White light emission from Mn2+ doped ZnS nanocrystals through the surface chelating of 8-hydroxyquinoline-5-sulfonic acid | |
| Wang et al. | Simple and greener synthesis of highly photoluminescence Mn2+-doped ZnS quantum dots and its surface passivation mechanism | |
| US7175778B1 (en) | Self-aligning QCA based nanomaterials | |
| Wang et al. | Synthesis of CdTe nanocrystals with mercaptosuccinic acid as stabilizer | |
| WO2007026746A1 (en) | Semiconductor nanoparticle and method for manufacturing same | |
| CN101787285A (en) | Method for preparing water-soluble fluorescent ZnSe/ZnS core-shell quantum dots | |
| Zou et al. | Aqueous phase synthesis of biostabilizer capped CdS nanocrystals with bright emission | |
| Chen et al. | Room-temperature ionic-liquid-assisted hydrothermal synthesis of Ag-In-Zn-S quantum dots for WLEDs | |
| Wang et al. | Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles | |
| CN108753284B (en) | High-fluorescence red light emission Mn: CsPbCl3Preparation method of nano-cluster | |
| CN110669506A (en) | Preparation method of water-soluble gold nanocluster fluorescent material jointly protected by cysteamine and N-acetyl L-cysteine | |
| Xu et al. | Seed-mediated growth approach for rapid synthesis of high-performance red-emitting CdTe quantum dots in aqueous phase and their application in detection of highly reactive oxygen species | |
| Du et al. | Synthesis and properties of ZnS quantum dots by an oil-water interface method | |
| Yuan et al. | Time-resolved photoluminescence spectroscopy evaluation of CdTe and CdTe/CdS quantum dots | |
| Wang et al. | High quality zinc-blende CdSe nanocrystals synthesized in a hexadecylamine–oleic acid–paraffin liquid mixture | |
| CN1912047A (en) | Method of packing CdTe nanometer crystal using microwave assisted water soluble polymer | |
| Wu et al. | Depositing ZnS shell around ZnSe core nanocrystals in aqueous media via direct thermal treatment | |
| Yang et al. | Phase transfer of hydrophobic QDs for water-soluble and biocompatible nature through silanization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070321 Termination date: 20120428 |