CN107573923A - A kind of nucleocapsid alloy quantum dot and preparation method thereof - Google Patents
A kind of nucleocapsid alloy quantum dot and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of nucleocapsid alloy quantum dot and preparation method thereof, and the preparation method comprises the following steps：Nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent are mixed, is incubated under 220~280 DEG C of nucleation temperatures, obtains quantum dot nucleome；Shelling temperature of the obtained quantum dot nucleome at 300~318 DEG C is mixed with shelling cationic source, shelling negative ion source and hydrocarbon organic solvent, obtains nucleocapsid alloy quantum dot.The present invention synthesizes quantum dot nucleus under lower temperature conditions, and high quantum production rate, the good core-shell quanta dots of stability are prepared in the method for subsequent higher temperature growth shell.
Description
Technical field
The present invention relates to nano-functional material technical field, more particularly to a kind of nucleocapsid alloy quantum dot and its preparation side
Method.
Background technology
Fluorescence quantum, especially II-VI race's semiconductor nano fluorescence quantum are study hotspots in recent years.Pass through regulation and control
Quantum dot size can produce the fluorescence of different wave length, this cause its biomolecular labeling and immune detection, light emitting diode,
The potential application of laser and solar cell etc. receives significant attention.
More further raisings that quanta point material optical stability is realized by quantum dot involucrum method in the prior art, with
Expand the application of quantum dot.Existing quantum dot involucrum method mainly has higher temperatures nucleation and relatively low-temperature epitaxy shell
SILAR method, specific method washed to add certain purification solvent after higher temperature obtains nuclear quantum dot
Wash and precipitate quantum dot, the quantum dot being settled out is dissolved in reaction dissolvent, alternately add involucrum reaction cationic source and the moon
Ion gun, the formation of new core is prevented, is grown at a lower temperature.Although the jacket operation of SILAR method is controllable
Property it is good, suitable for more class objects, but cumbersome, the step such as deposition and purification can make quantum dot surface produce change, cause
Existing defects between nucleome and Shell Materials, so as to influence quantum yield and stability, quantum dot is limited to a certain extent
The development of related application research and the large-scale production of product.
The content of the invention
It is an object of the invention to provide a kind of nucleocapsid alloy quantum dot and preparation method thereof.Preparation side provided by the invention
Method is simple to operate, and the nucleocapsid alloy quantum dot stability being prepared is good and quantum yield is high.
The invention provides the preparation method of nucleocapsid alloy quantum dot, comprise the following steps：
(1) nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent are mixed, is incubated, obtains in nucleation temperature
Quantum dot nucleome；The nucleation temperature is 220~280 DEG C；
(2) by the quantum dot nucleome that the step (1) obtains in shelling temperature and shelling cationic source, shelling negative ion source
Mixed with hydrocarbon organic solvent, carry out shelling reaction, obtain nucleocapsid alloy quantum dot；The shelling temperature is 300~318 DEG C；
The nucleation cationic source and shelling cationic source independently are zinc source and/or cadmium source；
The nucleation negative ion source and nucleation negative ion source independently are sulphur source and/or selenium source.
Preferably, when the structure of the shell includes multilayer shell, in addition to：Repeat in the step (2)
Shelling process；The number of the repetition shell number of plies few 1 than needed for.
Preferably, after the mixing in the step (2) or after the repetition shelling process, in addition to shell regrowth
Journey, it is specially：The mixed liquor being mixed to get or the mixed liquor for repeating to obtain after shelling process are incubated 1 at 330~340 DEG C
~4h.
Preferably, the mol ratio of the nucleation cationic source and nucleation negative ion source is (1~4)：1.
Preferably, the mol ratio of the quantum dot nucleome and shelling cationic source, shelling negative ion source is 1:(720~
2160):(600~1800).
Preferably, the zinc source is zinc salt；The sulphur source is alkyl hydrosulfide；The selenium source is selenium simple substance.
Preferably, the preparation of the nucleocapsid alloy quantum dot is carried out under inert gas or nitrogen protection.
Present invention also offers nucleocapsid alloy quantum dot prepared by preparation method described in above-mentioned technical proposal, there is nucleocapsid knot
Structure, including nucleome and the shell that is coated on outside the nucleome；The nucleome is CdS core body, CdSe core body, ZnSe core body or ZnS
Nucleome；The shell is CdS shells, CdSe shells, ZnSe shells, ZnS shells, ZnCdSe shells or CdZnS shells.
Preferably, the number of plies of the shell is 1,2,3,4 or 5.
Preferably, the particle diameter of the nucleome is 1.8~4.5nm, and the thickness of shell is 0.6~5nm.
The invention provides the preparation method of nucleocapsid alloy quantum dot, comprise the following steps：Will nucleation cationic source, nucleation
Negative ion source and hydrocarbon organic solvent mixing, are incubated under 220~280 DEG C of nucleation temperatures, obtain quantum dot nucleome；By what is obtained
Quantum dot nucleome mixes in 300~318 DEG C of shelling temperature with shelling cationic source, shelling negative ion source and hydrocarbon organic solvent
Close, carry out shelling reaction, obtain nucleocapsid alloy quantum dot.The present invention synthesizes quantum dot nucleus under the conditions of relatively lower temp,
The method of subsequent higher temperature growth shell is prepared high quantum production rate, chemical stability and the good nucleocapsid amount of light durability
Sub- point.
The present invention at 220~280 DEG C to be nucleated, and in 300~318 DEG C of shellings, shelling temperature is higher than nucleation temperature, is advantageous to
Shell cation or anion diffuse to form interface alloy to nuclear material, reduce the lattice mismatch between core-shell material, improve
Lattice fit, reduce defect generation；And because temperature is higher in growth course, Shell Materials crystallinity is preferable, reduce
The defects of being introduced in Shell Materials growth course, and then it is favorably improved the quantum yield and stability of core-shell quanta dots.
Preparation method provided by the invention is simple to operate, and the nucleocapsid alloy quantum dot stability being prepared is good and quantum
Yield is high, and it is relatively low to solve to prepare quantum yield at present, the problem of less stable.The result of embodiment shows prepared by the present invention
Obtained core-shell quanta dots stability is good, and quantum yield is not less than 90%.
Brief description of the drawings
Fig. 1 is that embodiment 1 prepares fluorescence spectrum variation diagram during ZnSe/ZnS nuclear shell structure quantum points；
Fig. 2 prepares the XRD spectrum variation diagram during ZnSe/ZnS nuclear shell structure quantum points for embodiment 1；
Fig. 3 prepares the electron microscope during ZnSe/ZnS nuclear shell structure quantum points for embodiment 1；
Fig. 4 is the ZnSe/ZnS core-shell quanta dots fluorescence patterns of different luminous peak positions prepared by embodiment 1；
Fig. 5 is that embodiment 2 prepares fluorescence spectrum variation diagram during CdSe/CdS nuclear shell structure quantum points；
Fig. 6 is that embodiment 3 prepares fluorescence spectrum variation diagram during CdSe/CdS/CdZnS nuclear shell structure quantum points；
Fig. 7 is that embodiment 4 prepares fluorescence spectrum variation diagram during CdSe/CdS/CdZnS/ZnS nuclear shell structure quantum points；
Fig. 8 is ZnSe/ZnS, CdSe/CdS, CdSe/CdS/CdZnS and CdSe/CdS/CdZnS/ZnS core shell structure quantum
Point is in different purifying time and the quantum yield situation of change in the case of different light application times.
Embodiment
The invention provides a kind of preparation method of nucleocapsid alloy quantum dot, comprise the following steps：
(1) nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent are mixed, is incubated, obtains in nucleation temperature
Quantum dot nucleome；The nucleation temperature is 220~280 DEG C；
(2) by the quantum dot nucleome that the step (1) obtains in shelling temperature and shelling cationic source, shelling negative ion source
Mixed with hydrocarbon organic solvent, carry out shelling reaction, obtain nucleocapsid alloy quantum dot；The shelling temperature is 300~318 DEG C；
The nucleation cationic source and shelling cationic source independently are zinc source and/or cadmium source；
The nucleation negative ion source and nucleation negative ion source independently are sulphur source and/or selenium source.
In the present invention, the nucleation cationic source and shelling cationic source independently are zinc source and/or cadmium source.In this hair
In bright, the zinc source is preferably zinc salt, more preferably organic acid zinc, more preferably zinc oleate, zinc stearate, capric acid zinc,
One or more in zinc laurate and tetradecylic acid zinc；The cadmium source is preferably cadmium salt, more preferably organic acid cadmium, more excellent
Elect the one or more in cadmium oleate, cadmium stearate, capric acid cadmium, cadmium laurate and tetradecylic acid cadmium as.
In the present invention, the nucleation negative ion source and nucleation negative ion source independently are sulphur source and/or selenium source.In this hair
In bright, the sulphur source is preferably alkyl hydrosulfide, more preferably tetraalkyl mercaptan, six alkyl hydrosulfides, ten alkyl hydrosulfides, 12
One or more in alkyl hydrosulfide and hexadecyl mercaptan；The selenium source is preferably selenium simple substance, more preferably selenium powder；This
Invention does not have particular/special requirement to the particle diameter of the selenium powder, using selenium powder well-known to those skilled in the art.
The present invention mixes nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent, is incubated, obtains in nucleation temperature
To quantum dot nucleome.In the present invention, the hydrocarbon organic solvent is preferably alkene organic solvent and/or alkane organic solvent；
The alkene organic solvent is preferably octadecylene；The alkane organic solvent preferably includes lignocerane.The present invention is to the alkene
The source of hydrocarbon organic solvent and alkane organic solvent does not have particular/special requirement, using well-known to those skilled in the art；
In the present invention, the alkane organic solvent is preferably provided with paraffin and/or mineral oil；The paraffin is more preferably liquid stone
Wax, the selection of the atoleine can reduce synthesis cost.The present invention is not special to the dosage of the hydrocarbon organic solvent
It is required that can realize that the dissolving to solute is defined；In an embodiment of the present invention, the volume of the hydrocarbon organic solvent is preferably
/ to three/10ths of reaction vessel volume.The hydrocarbon organic solvent environmental protection and cost that the present invention uses are low, can save
Cost more than 60%.
In the present invention, the mol ratio of the nucleation cationic source and nucleation negative ion source is preferably (1~4)：1, enter one
Step is preferably 2:1.
In the present invention, the mixing of the nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent preferably includes
Following steps：The nucleation cationic source and hydrocarbon organic solvent are mixed to get nucleation cationic source presoma；By it is described into
Core negative ion source is mixed to get nucleation negative ion source presoma with hydrocarbon organic solvent；Again by the obtained nucleation cationic source
Presoma and the presoma mixing of nucleation negative ion source.In the present invention, the nucleation cationic source presoma and nucleation anion
Source presoma mixing, preferably the nucleation cationic source presoma is injected into nucleation negative ion source presoma.The present invention
Nucleation cation presoma is injected into nucleation anion presoma, is advantageous to improve reactivity, and then help to form crystalline substance
The good nucleus of type.
In the present invention, the concentration of the nucleation cationic source presoma is preferably 0.1~0.6mol/L, further preferably
For 0.2mol/L, the 0.1~0.6mol/L of concentration, more preferably 0.24mol/L of the nucleation negative ion source presoma.
The present invention does not have particular/special requirement to the mode mixed described in above-mentioned technical proposal, ripe using those skilled in the art institute
The solution hybrid mode known.In the present invention, when it is selenium source to be nucleated negative ion source, the selenium source and hydrocarbon organic solvent
Mixing preferably carried out under the conditions of 200~220 DEG C；Hydrocarbon organic solvent for being mixed with selenium source is preferably octadecylene.
After the mixing for completing nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent, the present invention is mixed by what is obtained
Close liquid to be incubated in nucleation temperature, obtain quantum dot nucleome.In the present invention, the nucleation temperature is 220~280 DEG C, is preferably
225~275 DEG C, more preferably 230~270 DEG C, more preferably 240 DEG C.The present invention is in the nucleation temperature soaking time
Preferably 10~90min, more preferably 15~80min, more preferably 20~60min, most preferably 30~40min.This
In the nucleation temperature insulating process nuclear reaction occurs into for invention, obtains quantum dot nucleome.
The present invention is organic in shelling temperature and shelling cationic source, shelling negative ion source and hydro carbons by the quantum dot nucleome
Solvent mixes, and carries out shelling reaction, obtains nucleocapsid alloy quantum dot.In the present invention, the hydrocarbon organic solvent is preferably alkene
Hydrocarbon organic solvent and/or alkane organic solvent；The alkene organic solvent is preferably octadecylene；The alkane organic solvent is preferred
Including lignocerane.The present invention does not have particular/special requirement to the source of the alkene organic solvent and alkane organic solvent, using this
Known to art personnel；In the present invention, the alkane organic solvent is preferably carried with paraffin and/or mineral oil
For；The paraffin is more preferably liquid paraffin, and the selection of the atoleine can reduce synthesis cost.The present invention is to institute
The dosage for stating hydrocarbon organic solvent does not have particular/special requirement, can realize that the dissolving to solute is defined；In an embodiment of the present invention,
The volume of the hydrocarbon organic solvent is preferably 1st/1 to three/10ths of reaction vessel volume.The hydro carbons that the present invention uses
Organic solvent is environmentally friendly and cost is low, and cost-saved more than 60%.
In the present invention, the quantum dot nucleome and shelling cationic source, the mol ratio of shelling negative ion source are preferably 1:
(720~2160):(600~1800), more preferably 1:(800~2000):(700~1500), more preferably 1:(1000
~1500):(800~1200)；In the present invention, the mol ratio of the shelling cationic source and shelling negative ion source is more than 1.
In the present invention, the quantum dot nucleome and shelling cationic source, shelling negative ion source and hydrocarbon organic solvent
Mixing preferably includes following steps：(1) the shelling cationic source and hydrocarbon organic solvent are mixed, obtains shelling cationic source
Presoma；The shelling negative ion source and hydrocarbon organic solvent are mixed, obtain shelling negative ion source presoma；(2) by described in
Shelling cationic source presoma and the mixing of shelling negative ion source presoma, obtain shelling presoma；(3) by the shelling presoma
It is injected into the quantum dot nucleome.In the present invention, the concentration of the shelling cationic source presoma be preferably 0.1~
0.6mol/L, more preferably 0.2mol/L, the concentration of the shelling negative ion source presoma is preferably 0.1~0.6mol/
L, more preferably 0.24mol/L.
Mixing of the present invention to shelling cationic source and hydrocarbon organic solvent, shelling negative ion source and hydrocarbon organic solvent
Mixing and the no particular/special requirement of mixing of shelling cationic source presoma and shelling negative ion source presoma, using this area skill
Solution hybrid mode known to art personnel.When shelling negative ion source is selenium source, the selenium source and hydrocarbon organic solvent
Mixing preferably carried out under the conditions of 200~220 DEG C；Hydrocarbon organic solvent for being mixed with selenium source is preferably octadecylene.
In the present invention, the speed that the shelling presoma is injected into the quantum dot nucleome is preferably 3~10mL/h, is entered
One step is preferably 6mL/h.In the present invention, the injection mode is preferably to be added dropwise；Concrete operations of the present invention to the dropwise addition
Mode does not have particular/special requirement, using solution dropwise addition mode well-known to those skilled in the art.
In the present invention, the quantum dot nucleome and shelling cationic source, shelling negative ion source and hydrocarbon organic solvent
It is blended at a temperature of shelling and carries out；The shelling temperature is 300~318 DEG C, preferably 305~315 DEG C, is more preferably
308~310 DEG C.The present invention exists in the quantum dot nucleome and shelling cationic source, shelling negative ion source and hydrocarbon organic solvent
Shelling temperature mixing process, shelling reaction is carried out, realizes cladding of the shell in core surface.
The present invention can also preferably prepare the core-shell quanta dots with multilayer shell；When the structure of the nucleocapsid include it is more
During layer shell, in addition to：Repeat the shelling process.In the present invention, the shelling process and above-mentioned technical proposal institute
The shelling process stated is consistent, will not be repeated here.
When the present invention prepares the core-shell quanta dots with multilayer shell by repeating the shelling process, preferably it incite somebody to action this
The core-shell quanta dots obtained before secondary repeat step by shelling process are used as shelling nucleome again, in shelling temperature and shelling sun
Ion gun, shelling negative ion source and hydrocarbon organic solvent mixing carry out shelling.
In the present invention, in the shelling process repetitive process, shelling cationic source, shelling the moon for different shells from
The species of component and hydrocarbon organic solvent can be the same or different.In the present invention, the number of the repetition preferably compares
The required shell number of plies few 1；The number of the repetition is preferably 1 time, 2 times, 3 times or 4 times.
In the present invention, the quantum dot nucleome mixes with shelling cationic source, shelling negative ion source and hydrocarbon organic solvent
After conjunction, preferably also include shell regrowth process, be specially：The mixed liquor being mixed to get is incubated 1 at 330~340 DEG C
~4h.In the present invention, the holding temperature is 330~340 DEG C, preferably 335~338 DEG C；The soaking time be 1~
4h, preferably 1.5~3.5h, more preferably 2~3h.The present invention is at the insulation that the holding temperature carries out certain time
Reason, helps to be coated on the further growth of the shell of the core surface, further to improve quantum dot stability.
When preferred preparation of the invention has the core-shell quanta dots of multilayer shell, preferably also include the shell regrowth
Journey；Specially：The mixed liquor for repeating to obtain after shelling process described in above-mentioned technical proposal is incubated 1~4h at 330~340 DEG C；I.e.
The final mixed liquor obtained after multiple shelling process is incubated 1~4h at 330~340 DEG C.In the present invention, the holding temperature
For 330~340 DEG C, preferably 335~338 DEG C；The soaking time is 1~4h, preferably 1.5~3.5h, further preferably
For 2~3h.In the present invention, the shell regrowth process is consistent with the shell regrowth process described in above-mentioned technical proposal,
It will not be repeated here.
Shelling cationic source and shelling negative ion source are mixed and added by the present invention, are regenerated by mixing shelling-insulation shell
Growth process, the cladding of shell is realized, without adding stage by stage, can not only reduce the complex of operation, can also effectively mix
Zwitterion is closed, is more beneficial for Shell Materials growth.
The preparation method of nucleocapsid alloy quantum dot provided by the invention is preferably carried out under inert gas or nitrogen protection.
The preparation method of nucleocapsid alloy quantum dot provided by the invention, shelling cationic source and shelling negative ion source are mixed
Add, without shelling cation and anion are respectively adopted into syringe addition or friendship according in conventional shell growth course
For the mode of zwitterion is added, the complex of operation can be not only reduced, can also effectively mix zwitterion, more favorably
Grown in Shell Materials, method is simple, and solution prepares related core-shell quanta dots process complexity at present, severe reaction conditions, prepares
The problem of cost is high.
And method provided by the invention is different to close under the comparative high temperature not less than 300 DEG C in the prior art
Into quantum dot nucleome, then in a manner of growing shell under the relatively lower temp less than 300 DEG C, the present invention is in lower temperature conditions
High quantum production rate, the good nucleocapsid of stability is prepared in lower synthesis quantum dot nucleus, the method for subsequent higher temperature growth shell
Quantum dot.
Present invention also offers the nucleocapsid alloy quantum dot that preparation method described in above-mentioned technical proposal is prepared, and has core
Shell structure, including nucleome and the shell that is coated on outside the nucleome.In the present invention, the nucleome is CdS core body, CdSe core
Body, ZnSe core body or ZnS core body；The shell is CdS shells, CdSe shells, ZnSe shells, ZnS shells or CdZnS shells.
In the present invention, the number of plies of the shell is preferably 1,2,3,4 or 5.When there is multilayer shell, the group of different shells
Divide and can be the same or different.
In the present invention, the particle diameter of the nucleome is preferably 1.8~4.5nm, more preferably 2~4nm, more preferably
3nm；The thickness of the shell is preferably 0.6~5nm, more preferably 1.0~4.5nm, more preferably 1.2~4.0nm, most
Preferably 2~3.5nm.
In order to further illustrate the present invention, with reference to embodiment to nucleocapsid alloy quantum dot provided by the invention and its system
Preparation Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
0.16gSe powder and 20mL octadecylenes are mixed to join in 50mL three-necked bottle, obtained in 220 DEG C of heating faint yellow
Solution, it is standby as Se presomas；9mmol (5.643g) zinc oleate is dissolved in 30mL atoleines, as Zn presomas
It is standby；
Take 2mLSe presomas and 8mL atoleines to mix and be put into 100mL three-necked bottles, under nitrogen protection when being heated to 280
DEG C when, 1.3mL Zn presomas are injected into above-mentioned mixed solution, react 10min under the conditions of 280 DEG C, obtain ZnSe quantum
Point nucleome.
After solution after above-mentioned reaction 10min is warming up into 318 DEG C, then the Zn forerunner by the alkyl hydrosulfides of 2mL eight and 20mL
The mixed liquor of body is added drop-wise in 318 DEG C obtained above of solution, drop rate 6mL/h, is added dropwise to complete follow-up temperature of continuing rising and is existed
4h is incubated under the conditions of 340 DEG C and carries out shell growth, obtains ZnSe/ZnS nuclear shell structure quantum points.
Quantum yield test is carried out to the ZnSe/ZnS nuclear shell structure quantum points being prepared, quantum yield is 85 ± 5%.
Fluorometric investigation is carried out to the quantum dot for being incubated 1h, 2h, 4h under the conditions of ZnSe quantum dots core, 340 DEG C respectively, respectively such as
In Fig. 1 fluorescence spectrum variation diagrams shown in a, b, c and d.As shown in Figure 1, as can be seen from the figure with the extension in reaction time,
The generation blue shift of Fluorescent peal slightly, while fluorescence peak half-peak breadth narrows.
The quantum nucleome to different growth times and different growth time inner capsid quantum dots carry out XRD analysis respectively,
Shown in result figure 2, a, b are XRD spectrum when ZnSe quantum dots core grows 3min, 10min respectively in Fig. 2, and c, d, e are respectively
ZnS shells form ZnSe/ZnS XRD spectrum when growing 1h, 2h, 4h.As shown in Figure 2, ZnSe and different time sampling is arrived
ZnSe/ZnS nuclear shell structure quantum points are zincblende lattce structure crystal formation, and crystallinity is good, with the extension XRD in reaction time
Collection of illustrative plates peak position gradually moves to wide-angle, illustrates that Shell Materials ZnS grows successfully, and thickness gradually increases.
The ZnS shells of quantum dot to being incubated 1h, 2h, 4h under the conditions of ZnSe quantum dots core and 340 DEG C respectively carry out saturating
Radio sem observation, as a result respectively as shown in a, b, c and d in Fig. 3.From the figure 3, it may be seen that the extension ZnSe/ZnS cores with the reaction time
Core-shell structure quantum dots gradually increase relative to the size of ZnSe nucleus in figure a, demonstrate again that the successful growth of ZnS shells, simultaneously
The quantum dot that different time obtains, which can be seen that, has suffered homogeneity and dispersiveness that quantum dot in growth course keeps good.
According to the nucleation process preparation amount daughter nucleus body in the present embodiment, difference is the soaking time difference at 280 DEG C, obtains
To different ZnSe quantum dot nucleomes.Respectively to react 3min, 5min, 15min, 30min and 80min under the conditions of 280 DEG C after
ZnSe be quantum nucleome ZnSe/ZnS core-shell quanta dots are prepared, respectively carry out fluorescence pattern analysis, as a result as shown in figure 4,
In Fig. 4 on the basis of 5 curve peaks, it is 410,418,426,436 and 452nm's from left to right to correspond to Fluorescent peal respectively
ZnSe/ZnS core shell structures.As shown in Figure 4, the fluorogram for the ZnSe/ZnS core-shell quanta dots being prepared with different quantum dot cores
Spectrum can cover 400~455nm.
Embodiment 2
By 7.294g cadmium oleates, 100 DEG C are dissolved in 30mL atoleines, standby as nucleation cationic source Cd presomas；
Take 1mmol Se powder to be mixed to join with 20mL atoleines in 100mL three-necked bottles, be warming up to 240 DEG C, inject Cd
Presoma 5mL, CdSe quantum dot core is obtained after reacting 30min under the conditions of 240 DEG C.
Be warming up to be added dropwise after 310 DEG C 10mL through 1.351g cadmium oleates be dissolved in Cd presomas that 10mL atoleines obtain with
The mixture of the alkyl hydrosulfides of 0.5mL ten, drop rate 10mL/h, after dripping off, react 4h at 330 DEG C.Finally give CdSe/
CdS core shell quantum dot.
Quantum yield test, quantum yield 90% are carried out to the CdSe/CdS nuclear shell structure quantum points being prepared.
The quantum nucleome to different growth times and different growth time inner capsid quantum dots carry out fluorometric investigation respectively,
Fluorescence spectrum variation diagram is as shown in figure 5, wherein a, b are respectively fluorescent absorption figure when CdSe quantum dot grows 10min, 30min
Spectrum, fluorescent absorption collection of illustrative plates when c, d are respectively CdS shells growth 1h, 2h.As shown in Figure 5, fluorescence is inhaled during coating CdS shells
Receive peak position and red shift gradually occurs, it was demonstrated that successful growth of the CdS shells on CdSe surfaces, form CdSe/CdS core shell structures.
Embodiment 3
By 7.294g cadmium oleates, 100 DEG C are dissolved in 30mL atoleines, standby as nucleation cationic source Cd presomas.Take
1mmol Se, 50mL octadecylenes are mixed to join 250mL three-necked bottles, heat up 240 DEG C, the injection foregoing obtained nucleation sun of 5mL from
Component Cd presomas, CdSe quantum dot is obtained after reacting 30min at 240 DEG C.
1.351g cadmium oleates are dissolved in 10mL atoleines, obtain shelling cationic source Cd presomas；By what is obtained
After CdSe quantum dot is warming up to 300 DEG C, 10mL shelling cationic source Cd presomas and 0.6mL dodecyls are added dropwise at 300 DEG C
The mixture of mercaptan, speed 3mL/h, obtain CdSe/CdS core-shell quanta dots.
318 DEG C are continuously heating to, while 0.203g zinc oleates are dissolved in 3mL atoleines as shelling cationic source Zn
Presoma, 0.188g cadmium oleates are dissolved in 3mL atoleines as shelling cationic source Cd presomas.To being warming up to 318 DEG C
Mixture 3mL shelling cationic source Zn presomas, 3mL shellings cationic source Cd presomas and the alkyl hydrosulfides of 0.7mL eight is added dropwise
Mixture, drop rate 6mL/h, after dripping off 340 DEG C react 4h.Finally give CdSe/CdS/CdZnS nucleocapsid quantum
Point.
Quantum yield test is carried out to the CdSe/CdS/CdZnS nuclear shell structure quantum points being prepared, quantum yield is
93%.
The quantum nucleome to different growth times and different growth time inner capsid quantum dots carry out fluorometric investigation respectively,
Fluorescence spectrum variation diagram is as shown in fig. 6, wherein, a, b are respectively fluorescent absorption figure when CdSe quantum dot grows 10min, 30min
Spectrum, c are fluorescent absorption collection of illustrative plates when CdS shells are added dropwise, and d is that 340 DEG C of reaction 4h are that fluorescence is inhaled when CdZnS shells grow 4h
Receive collection of illustrative plates.
It will be appreciated from fig. 6 that CdS shells be added dropwise rear fluorescent absorption peak position (Fig. 6 c) relative to Fig. 6 b have one it is larger red
Move, show the successful growth of CdS shells, then growth finishes the further red shift of fluorescent absorption peak position after the addition of CdZnS shells
Illustrate the growth success of CdZnS shells.
Embodiment 4
By 7.294g cadmium oleates, 100 DEG C are dissolved in 30mL atoleines, standby as nucleation cationic source Cd presomas.Take
1mmol Se, 50mL atoleines are mixed to join in 250mL three-necked bottles, are heated up 240 DEG C, injection 5mL nucleation cationic sources Cd
Presoma, 240 DEG C reaction 30min after CdSe quantum dot.
1.351g cadmium oleates are dissolved in 10mL atoleines, obtain shelling cationic source Cd presomas；By what is obtained
CdSe quantum dot is warming up to 300 DEG C, and the mixture of 10mL shellings cationic source Cd presomas and the alkyl hydrosulfides of 0.6mL eight is added dropwise,
Drop rate is 6mL/h, coats CdS shells；It is continuously heating to 310 DEG C and 3mL shelling cationic source Zn presomas (warp is added dropwise
0.203g zinc oleates are dissolved in 3mL atoleines and obtained), 3mL shelling cationic source Cd presomas (through 0.188g cadmium oleates dissolve
Obtained in 3mL atoleines) with the mixtures of the alkyl hydrosulfides of 0.7mL six, drop rate 6mL/h, coat CdZnS shells；Connect
Dropwise addition 4mL shelling cationic source Zn presomas after being warming up to 330 DEG C (to be dissolved in 4mL atoleines through 1.005g zinc oleates to obtain
To) with the mixture of 0.4mL tetraalkyl mercaptan, drop rate 6mL/h, drip off and react 4h under the conditions of 330 DEG C.Final
To CdSe/CdS/CdZnS/ZnS core-shell quanta dots.
Quantum yield test, quantum yield are carried out to the CdSe/CdS/CdZnS/ZnS nuclear shell structure quantum points being prepared
For 95%.
Fluorometric investigation is carried out to quantum dot core and core-shell quanta dots, fluorescence spectra is as shown in Figure 7.Wherein, a is CdSe amounts
The fluorescent absorption collection of illustrative plates of son point nucleus, b are fluorescent absorption collection of illustrative plates after cladding CdS shells, and c inhales for fluorescence after cladding CdZnS shells
Collection of illustrative plates is received, d is fluorescent absorption collection of illustrative plates after cladding ZnS shells.As shown in Figure 7, rear fluorescent absorption peak position phase is added dropwise in CdS shells
There is a larger red shift for the fluorescent absorption peak position of CdSe nucleus in Fig. 7 a, show the successful growth of CdS shells, then exist
Growth finishes the growth success that the further red shift of fluorescent absorption peak position illustrates CdZnS shells after CdZnS shells add, subsequent
Occur blue shift slightly during growth ZnS, be because the result that the Zn elements in ZnS shells permeate to nexine, it was demonstrated that ZnS
Successful cladding.
Embodiment 5
Core-shell quanta dots are prepared in the way of embodiment 1, difference is to be incubated after need not continuing heating after being added dropwise to complete
Shell growth course, obtain ZnSe/ZnS nuclear shell structure quantum points.
Quantum yield test is carried out to the core-shell quanta dots being prepared, quantum yield can be obtained as 81%.
Embodiment 6
By 7.294g cadmium oleates, 100 DEG C are dissolved in 30mL atoleines, standby as nucleation cationic source Cd presomas.Take
1mmol Se, 50mL octadecylenes are mixed to join 250mL three-necked bottles, heat up 240 DEG C, the injection foregoing obtained nucleation sun of 5mL from
Component Cd presomas, CdSe quantum dot is obtained after reacting 30min at 240 DEG C.
1.351g cadmium oleates are dissolved in 10mL atoleines, obtain shelling cationic source Cd presomas；By what is obtained
After CdSe quantum dot is warming up to 300 DEG C, 10mL shelling cationic source Cd presomas and 0.6mL dodecyls are added dropwise at 300 DEG C
The mixture of mercaptan, drop rate 6mL/h, obtain CdSe/CdS core-shell quanta dots.
318 DEG C are continuously heating to, while 0.203g zinc oleates are dissolved in 3mL atoleines as shelling cationic source Zn
Presoma, 0.188g cadmium oleates are dissolved in 3mL atoleines as shelling cationic source Cd presomas.To being warming up to 318 DEG C
Mixture 3mL shelling cationic source Zn presomas, 3mL shellings cationic source Cd presomas and the alkyl hydrosulfides of 0.7mL eight is added dropwise
Mixture, drop rate 6mL/h.Finally give CdSe/CdS/CdZnS core-shell quanta dots.
Quantum yield test is carried out to the CdSe/CdS/CdZnS nuclear shell structure quantum points being prepared, quantum yield is
88%.
Embodiment 7
Quantum dot is dissolved using 10mL chloroform, then adds 30~40mL acetone soln, then using centrifuge
The method that quantum dot is precipitated out, the ZnSe/ZnS that embodiment 1~4 is prepared respectively, CdSe/CdS, CdSe/CdS/
CdZnS and CdSe/CdS/CdZnS/ZnS core-shell quanta dots are purified, so different numbers repeatedly, the amount being prepared respectively
Son point is repeatedly purified.The quantum dot yield of quantum dot after different purifying numbers is tested, difference purifying number situation
Lower quantum yield situation of change is as shown in a in Fig. 8.
ZnSe/ZnS, CdSe/CdS, CdSe/CdS/CdZnS and the CdSe/CdS/ that embodiment 1~4 is prepared respectively
Quantum yield of the CdZnS/ZnS core-shell quanta dots after the illumination of different time is tested, and quantum dot is in different light application times
In the case of quantum yield situation of change as shown in b in Fig. 8.
From a in Fig. 8, after multiple purification process, quantum yield is stablized constant, it is seen that the quantum dot being prepared
Chemical stability is good；From b in Fig. 8, obvious reduction occurs yet for the photo-irradiation treatment through different time, quantum yield,
It can be seen that quantum dot light durability is good.
As can be seen from the above embodiments, nucleocapsid alloy quantum dot quantum yield provided by the invention is high, and absorption spectrum goes out
Now more exciton peaks, fluorescence spectrum half-peak width, monochromaticjty is good, and good in different purifying numbers and light conditions stability inferior.
Described above is only the preferred embodiment of the present invention, not makees any formal limitation to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nucleocapsid alloy quantum dot, comprises the following steps：
(1) nucleation cationic source, nucleation negative ion source and hydrocarbon organic solvent are mixed, is incubated in nucleation temperature, obtains quantum
Point nucleome；The nucleation temperature is 220~280 DEG C；
(2) by the quantum dot nucleome that the step (1) obtains in shelling temperature and shelling cationic source, shelling negative ion source and hydrocarbon
Class organic solvent mixes, and carries out shelling reaction, obtains nucleocapsid alloy quantum dot；The shelling temperature is 300~318 DEG C；
The nucleation cationic source and shelling cationic source independently are zinc source and/or cadmium source；
The nucleation negative ion source and nucleation negative ion source independently are sulphur source and/or selenium source.
2. preparation method according to claim 1, it is characterised in that when the structure of the shell includes multilayer shell
When, in addition to：Repeat the shelling process in the step (2)；The number of the repetition shell number of plies few 1 than needed for.
3. preparation method according to claim 1 or 2, it is characterised in that after the mixing in the step (2) or described heavy
After multiple shelling process, in addition to shell regrowth process, it is specially：By the mixed liquor being mixed to get or repeat shelling process
The mixed liquor obtained afterwards is incubated 1~4h at 330~340 DEG C.
4. preparation method according to claim 1, it is characterised in that the nucleation cationic source and nucleation negative ion source
Mol ratio is (1~4)：1.
5. preparation method according to claim 1, it is characterised in that the quantum dot nucleome and shelling cationic source, into
The mol ratio of shell negative ion source is 1:(720~2160):(600~1800).
6. preparation method according to claim 1, it is characterised in that the zinc source is zinc salt；The sulphur source is alkyl sulfide
Alcohol；The selenium source is selenium simple substance.
7. preparation method according to claim 1, it is characterised in that the preparation of the nucleocapsid alloy quantum dot is in indifferent gas
Body or the lower progress of nitrogen protection.
8. nucleocapsid alloy quantum dot prepared by preparation method described in claim 1~7 any one, including nucleome and it is coated on institute
State the shell of nucleome outer surface；The nucleome is CdS core body, CdSe core body, ZnSe core body or ZnS core body；The shell is CdS
Shell, CdSe shells, ZnSe shells, ZnS shells, ZnCdSe shells or CdZnS shells.
9. nucleocapsid alloy quantum dot according to claim 8, it is characterised in that the number of plies of the shell be 1,2,3,4 or
5。
10. nucleocapsid alloy quantum dot according to claim 9, it is characterised in that the particle diameter of the nucleome be 1.8~
4.5nm, the thickness of shell is 0.6~5nm.
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