CN100523119C - Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal - Google Patents
Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal Download PDFInfo
- Publication number
- CN100523119C CN100523119C CNB2006100156049A CN200610015604A CN100523119C CN 100523119 C CN100523119 C CN 100523119C CN B2006100156049 A CNB2006100156049 A CN B2006100156049A CN 200610015604 A CN200610015604 A CN 200610015604A CN 100523119 C CN100523119 C CN 100523119C
- Authority
- CN
- China
- Prior art keywords
- cdte
- water
- aqueous solution
- shell
- quantum dot
- 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 water phase preparation process of water soluble nanometer CdTe/Cd(OH)2 crystal grain in core-shell structure is disclosed. The prepared water soluble nanometer CdTe/Cd(OH)2 crystal grain in core-shell structure has stable property, adjustable spectral range and high quantum yield. Hydrophilic mercaptan as stabilizer, cheap inorganic salt CdCl2 and Te powder are reacted in water solution to produce no-oxygen KHTe, which is heated and refluxed to produce water soluble nanometer CdTe particle. The water soluble nanometer CdTe particle and NaOH solution are reacted in hot bath for certain time determined by the thickness of Cd(OH)2 shell to produce quantum dot, which may have different sizes and different colors. The preparation process has relaxed condition, short production period, low cost, high quantum yield and other advantages, and the prepared modified particle may be used as probe in chemical, physical, biological, medical and other fields.
Description
[technical field]:
The present invention relates to a kind of preparing technical field of quantum dot, particularly synthetic high-quality water-soluble CdTe/Cd (OH) under simple and easy mild conditions
2The method of quantum dot.It is adjustable that this quantum dot has spectrum, quantum yield height, the characteristics of stable in properties.
[background technology]:
Quantum dot mainly be by II-IV family element (as CdSe, CdTe, CdS, ZnSe) and III-V family element (as InP, InAs) form, be generally sphere or class sphere, particle diameter is the particle of 1-12nm.Quantum dot is owing to particle diameter very little (about 1-30nm), and can be with continuously to become the discrete energy levels structure with molecular characterization, so its optics behavior being very similar to some macromole (as polycyclic aromatic hydrocarbon) by quantum confinement in electronics and hole, can emitting fluorescence.Because the influence that spectrum is prohibited, when the diameter of these quantum dots during less than its Bohr's diameter, will show special physics and chemical property, such as the size quantum effect, the dielectric confinement effect, and derive the characteristics of luminescence of quantum dot uniqueness thus, it is had broad application prospects at aspects such as luminescent material, photosensors.CdS, CdSe, quantum dots such as CdTe have special and good visible region fluorescent emission character, and its fluorescence intensity is strong, bleaching speed is slow, fluorescence spectrum is narrow, highly sensitive, and excitation spectrum continuous distribution, the fluorescence spectra position can be regulated and control by the size that changes quantum dot, and its emmission spectrum is crossed over the visible range, can be at the different quantum dot of a certain wavelength simultaneous excitation, obtain the different visible emissivity spectrum of wide region, carry out multiplex fluorescence and detect.These characteristics make quantum dot can be used as the novel fluorescent marker of a class, have broad application prospects in biomolecules identification and in detecting.
Adopt the synthetic quantum dot of chemical process to mainly contain Organometallic Chemistry method and aqueous phase synthesis method at present.
The Organometallic Chemistry method is a kind of chemical process of synthetic quantum dot commonly used.This method is normally under the condition of anhydrous and oxygen-free, in having the organic solvent environment of coordination character, grow into nanocrystal with metallorganics, be about to precursor and be injected in the high boiling tensio-active agent, by the nucleation and growth process of temperature of reaction control particulate.Its shortcoming of quantum dot of this method preparation is that preparation condition is relatively harsher, and reactions steps is more complicated also, the reagent cost height, and toxicity is bigger.And the semi-conductor nano particles that the organic synthesis method makes is transferred to water, and its step is more loaded down with trivial details, and quantum yield, the stability of the quantum dot aqueous solution that obtains after the processing reduce greatly.In recent years, direct demand of synthesizing the semi-conductor nano particles of excellent property in the aqueous solution increased day by day.The ultimate principle of aqueous phase synthesis method is to add stablizer (as sulfhydryl compound etc.) in water, obtains nanoparticle by the water ion exchange reaction.Its reaction conditions gentleness, simple to operate, toxicity is little, cost is low.Because nanoparticle is directly at the aqueous phase synthetic, has solved the water-soluble problem of nanoparticle, and narrow size distribution.But because the usually easy oxidation of quantum dot, the instability of preparation, and there are a large amount of defectives on the surface, has a strong impact on its quantum yield.
[summary of the invention]:
Purpose of the present invention is exactly that the Organometallic Chemistry method that solves existing quantum dot exists the preparation condition harshness, the reactions steps complexity, the reagent cost height, toxicity is bigger, and the water transfer step is more loaded down with trivial details, the quantum yield of the quantum dot aqueous solution that obtains after handling, the problem that stability reduces greatly; Solve the easy oxidation of quantum dot, the instability of aqueous phase synthesis method preparation simultaneously, and the surface there are a large amount of defectives, have a strong impact on the problem of its quantum yield.A kind of water-soluble core/shell-type CdTe/Cd is provided (OH)
2The aqueous phase preparation method of nanocrystal.
Water-soluble core/shell-type CdTe/Cd provided by the invention (OH)
2The aqueous phase preparation method of nanocrystal comprises successively:
(a) in closed reaction vessel, adding mol ratio is the KBH of 2:1
4With the Te powder, add the redistilled water of 1～4mL, normal-temperature reaction 40～80min under the magnetic agitation makes the transparent liquid of lilac, i.e. the KHTe aqueous solution of fresh anaerobic;
(b) CdCl
2Preparation with the L-halfcystine aqueous solution: the 0.01～0.02molL that gets 15mL～25mL
-1CdCl
2The aqueous solution adds redistilled water and the 0.0007～0.0012mol stablizer L-halfcystine of 25mL～45mL, with 3～5mol L in beaker
-1The NaOH aqueous solution regulate pH 11.0～12.0.
(c) add (b) in the there-necked flask of 250mL and go on foot the CdCl that contains for preparing
2With the aqueous solution 40～70mL of L-halfcystine, 20～30min is stirred in argon shield;
(d) get the KHTe aqueous solution of the fresh anaerobic of preparation in an amount of (a) step, join in (c) step, keeping the mol ratio of Cd:Te:L-cysteine is 2:1:4～5;
(e) (d) step in mixing solutions be heated to 92～96 ℃, back flow reaction 0～15min, centrifugal, get supernatant liquid and can obtain the CdTe quantum dot of yardstick than homogeneous;
(f) get the CdTe solution that 2～5mL (e) step prepares, add 2～5mL 0.5mol L
-1NaOH solution (pH=11-13), make Cd excessive in the solution
2+With OH
-Surface at CdTe nuclear forms Cd (OH)
2Shell, the warm respectively time of bathing 0～118min just can make size at the Cd of 2.7nm～4.4nm (OH) in 80～92 ℃ of water-baths
2The CdTe quantum dot that coats.
Advantage of the present invention and effect: method provided by the invention does not need harsh equipment, condition; simple and safe operation; toxicity is little, cost is low; used plant and instrument is common equipment; as: agitator, nitrogen protection device, three-necked bottle, reflux condensing tube, thermometer and the whizzer of band thermal source, its production cost is low, and reaction conditions is simple; reflux gets final product, and does not have the exacting terms requirement.
By being controlled at the CdTe/Cd (OH) that the easy water-bath method of employing has realized at aqueous phase controlledly synthesis different size under the alkaline condition
2Quantum dot, the water-bath time is long more, Cd (OH)
2Shell thickness, and the particle diameter of quantum dot big more, thereby can obtain changing to the quantum dot of orange-red several different colours by blue-greenish colour, realize that fluorescence spectrum is adjustable.Owing to coat the bigger semiconductor material Cd (OH) of band gap on the CdTe surface
2, make the core/shell type nanocrystal, strengthened its stability, and surperficial radiationless recombinable site is passivated, excite defective to improve its photoluminescent property greatly thereby reduce.So this quantum dot also has quantum yield height, the characteristics of stable in properties simultaneously.
[embodiment]:
Embodiment 1
(a) airtight, have in the reaction vessel of needle applicator, add 16.3mg KBH
4, the redistilled water of 19.2mgTe and 1.2mL, normal-temperature reaction 50min under the magnetic agitation makes the transparent liquid of lilac, i.e. the KHTe aqueous solution of fresh anaerobic;
(b) add the CdCl that contains for preparing in the there-necked flask of 250mL
2(get the 0.02mol L of 15mL with the aqueous solution of L-halfcystine
-1CdCl
2The aqueous solution adds redistilled water and the 0.0007mol L-halfcystine of 25mL in beaker, use 5mol L
-1The NaOH aqueous solution regulate pH about 11.20), 30min is stirred in argon shield;
(c) with the KHTe aqueous solution of prepared fresh among a, get and join in right amount among the b, keeping the mol ratio of Cd:Te:L-cysteine is 2:1:4.8.
(d) mixing solutions among the c is heated to 96 ℃, back flow reaction 15min.Centrifugal, get supernatant liquid and can obtain the CdTe quantum dot of yardstick than homogeneous.
(e) after the synthetic quantum dot CdTe, still there is excessive Cd in the solution
2+Get the CdTe solution that 2mL prepares, add 2mL 0.5mol L
-1NaOH solution (pH=11-13), excessive Cd in the solution like this
2+Will with OH
-Surface at CdTe nuclear forms Cd (OH)
2Shell, temperature is bathed the different time of 0～118min respectively in 92 ℃ of water-baths, just can make the CdTe/Cd (OH) of different size
2Quantum dot.
Embodiment 2
(a) airtight, have in the reaction vessel of needle applicator, add 51.5mgKBH
4, the redistilled water of 57.4mgTe and 3mL, normal-temperature reaction 70min under the magnetic agitation makes the transparent liquid of lilac, i.e. the KHTe aqueous solution of fresh anaerobic;
(b) add the CdCl that contains for preparing in the there-necked flask of 250mL
2(get the 0.02mol L of 20mL with the aqueous solution of L-halfcystine
-1CdCl
2The aqueous solution adds redistilled water and the 0.0096mol L-halfcystine of 33mL in beaker, use 5mol L
-1The NaOH aqueous solution regulate pH about 11.20), 30min is stirred in argon shield;
(c) with the KHTe aqueous solution of prepared fresh among a, get and join in right amount among the b, keeping the mol ratio of Cd:Te:L-cysteine is 2:1:4.8.
(d) mixing solutions among the c is heated to 96 ℃, back flow reaction 20min.Centrifugal, get supernatant liquid and can obtain the CdTe quantum dot of yardstick than homogeneous.
(e) after the synthetic quantum dot CdTe, still there is excessive Cd in the solution
2+Get the CdTe solution that 2mL prepares, add 2mL 0.5mol L
-1NaOH solution (pH=11-13), excessive Cd in the solution like this
2+Will with OH
-Surface at CdTe nuclear forms Cd (OH)
2Shell, temperature is bathed the different time of 0～118min respectively in 92 ℃ of water-baths, just can make the CdTe/Cd (OH) of different size
2Quantum dot.
Claims (1)
1, a kind of water-soluble core/shell-type CdTe/Cd (OH)
2The aqueous phase preparation method of nanocrystal is characterized in that this method comprises successively:
(a) in closed reaction vessel, adding mol ratio is the KBH of 2:1
4With the Te powder, add the redistilled water of 1～4mL, normal-temperature reaction 40～80min under the magnetic agitation makes the transparent liquid of lilac, i.e. the KHTe aqueous solution of fresh anaerobic;
(b) CdCl
2Preparation with the L-halfcystine aqueous solution: the 0.01～0.02mol L that gets 15mL～25ml
-1CdCl
2The aqueous solution adds redistilled water and the 0.0007～0.0012mol stablizer L-halfcystine of 25mL～45ml, with 3～5molL in beaker
-1The NaOH aqueous solution regulate pH 11.0～12.0;
(c) add (b) in the there-necked flask of 250mL and go on foot the CdCl that contains for preparing
2With the aqueous solution 40～70mL of L-halfcystine, 20～30min is stirred in argon shield;
(d) get the KHTe aqueous solution of the fresh anaerobic of preparation in an amount of (a) step, join in (c) step, keeping the mol ratio of Cd:Te:L-halfcystine is 2:1:4～5;
(e) (d) step in mixing solutions be heated to 92～96 ℃, back flow reaction greater than 0min to equaling 15min, centrifugal, get supernatant liquid and promptly obtain the CdTe quantum dot of yardstick than homogeneous;
(f) get the CdTe solution that 2～5mL (e) step prepares, add 2～5mL0.5mol L
-1NaOH solution, pH=11-13 makes Cd excessive in the solution
2+With OH
-Surface at CdTe nuclear forms Cd (OH)
2Shell, temperature is bathed in 80～92 ℃ of water-baths, and the warm bath time to equaling 118min, just can make size at the Cd of 2.7nm～4.4nm (OH) greater than 0min
2The CdTe quantum dot that coats.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100156049A CN100523119C (en) | 2006-09-07 | 2006-09-07 | Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100156049A CN100523119C (en) | 2006-09-07 | 2006-09-07 | Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1927994A CN1927994A (en) | 2007-03-14 |
| CN100523119C true CN100523119C (en) | 2009-08-05 |
Family
ID=37858131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100156049A Expired - Fee Related CN100523119C (en) | 2006-09-07 | 2006-09-07 | Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100523119C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101196461B (en) * | 2007-03-17 | 2010-05-19 | 广西师范大学 | Method for measuring CdTe quantum point grain diameter by resonant vibration scattered spectrum |
| TWI453161B (en) * | 2009-11-11 | 2014-09-21 | Univ Nat Chunghsing | Hydrophilic modified II-VI quantum dots and preparation method thereof |
| CN103087717B (en) * | 2012-12-10 | 2014-11-12 | 华中农业大学 | Preparation method of quantum dot solution with core-shell structure |
Citations (6)
| 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 |
| US20020066401A1 (en) * | 2000-10-04 | 2002-06-06 | Xiaogang Peng | Synthesis of colloidal nanocrystals |
| US20030148544A1 (en) * | 2001-06-28 | 2003-08-07 | Advanced Research And Technology Institute, Inc. | Methods of preparing multicolor quantum dot tagged beads and conjugates thereof |
| CN1693207A (en) * | 2005-04-28 | 2005-11-09 | 复旦大学 | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point by microwave radiation reaction |
| CN1693206A (en) * | 2005-04-28 | 2005-11-09 | 复旦大学 | Process for preparing water soluble cadmium telluride quantum point with program controlling microwave |
| CN1793923A (en) * | 2005-12-22 | 2006-06-28 | 复旦大学 | Preparation method of water soluble CdTe/CdS nuclear/shell type quantum point |
-
2006
- 2006-09-07 CN CNB2006100156049A patent/CN100523119C/en not_active Expired - Fee Related
Patent Citations (6)
| 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 |
| US20020066401A1 (en) * | 2000-10-04 | 2002-06-06 | Xiaogang Peng | Synthesis of colloidal nanocrystals |
| US20030148544A1 (en) * | 2001-06-28 | 2003-08-07 | Advanced Research And Technology Institute, Inc. | Methods of preparing multicolor quantum dot tagged beads and conjugates thereof |
| CN1693207A (en) * | 2005-04-28 | 2005-11-09 | 复旦大学 | Process for preparing water soluble CdTe/CdS nuclear/shell type quantum point by microwave radiation reaction |
| CN1693206A (en) * | 2005-04-28 | 2005-11-09 | 复旦大学 | Process for preparing water soluble cadmium telluride quantum point with program controlling microwave |
| CN1793923A (en) * | 2005-12-22 | 2006-06-28 | 复旦大学 | Preparation method of water soluble CdTe/CdS nuclear/shell type quantum point |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1927994A (en) | 2007-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106479482B (en) | InP quantum dots and preparation method thereof | |
| CN100572500C (en) | The aqueous phase preparation method of cyclodextrin modified CdTe quantum dot | |
| Wang et al. | Aqueous synthesis of mercaptopropionic acid capped Mn 2+-doped ZnSe quantum dots | |
| Liu et al. | Water-soluble lanthanides doped fluoride nanocrystals for biolabeling: Materials and photophysics | |
| Li et al. | Hydrothermal synthesis of highly luminescent CdTe quantum dots by adjusting precursors’ concentration and their conjunction with BSA as biological fluorescent probes | |
| Che et al. | Aqueous synthesis of high bright and tunable near-infrared AgInSe2–ZnSe quantum dots for bioimaging | |
| CN105295921A (en) | Preparation method of quaternary quantum dot CdSe@ZnS | |
| CN102071027B (en) | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof | |
| CN112080278B (en) | Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof | |
| CN102517003A (en) | Hydro-thermal preparation method for novel near infrared water-soluble copper-indium-sulfur three-element quantum dots | |
| CN101215471A (en) | Method for preparing water soluble fluorescence CdSe quantum dots used for showing fingerprint | |
| CN105154084A (en) | Preparation method for color-adjustable ternary AgInSe2 fluorescent quantum dots through aqueous-phase synthesis | |
| CN100523119C (en) | Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal | |
| Ansari et al. | Influence of shell formation on morphological structure, optical and emission intensity on aqueous dispersible NaYF4: Ce/Tb nanoparticles | |
| CN102634336A (en) | Luminescence-adjustable ligand-free cadmium sulfide semiconductor quantum dot and preparation method thereof | |
| Shen et al. | Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange | |
| Wang et al. | Nanocomposites of CsPbBr3 perovskite quantum dots embedded in Gd2O3: Eu3+ hollow spheres for LEDs application | |
| Langyan et al. | Photophysical properties of highly green luminescent Tb (III) complexes | |
| CN100494309C (en) | Synthesis method of core/shell type cadmium telluride/cadmium sulfide water-soluble quantum dot | |
| Xiao et al. | Multifunctional CaF2: Yb3+, Ho3+, Gd3+ nanocrystals: insight into crystal growth and properties of upconversion luminescence, magnetic, and temperature sensing properties | |
| 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 | |
| Cui et al. | Comparison of two strategies for the synthesis of upconverting nanoparticles as biological labels | |
| CN111718714A (en) | Cs (volatile organic Compounds)4PbBr6Zero-dimensional perovskite nano material and preparation method and application thereof | |
| Bao et al. | Luminescent properties of YVO 4: Eu/SiO 2 core–shell composite particles | |
| Wu et al. | Controllable synthesis of novel luminescent CuFeS 2 quantum dots with magnetic properties and cation sensing features |
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: 20090805 Termination date: 20100907 |