CN105967154A - Preparation method of monodisperse II-VI family quantum dot - Google Patents
Preparation method of monodisperse II-VI family quantum dot Download PDFInfo
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Abstract
The invention provides a preparation method of a monodisperse II-VI family quantum dot. The preparation method comprises S1, adding fatty acid into a system containing II-VI family quantum dot seed crystals so that the II-VI family quantum dot seed crystals and fatty acid are mixed and undergo a reaction at a temperature of 200-300 DEG C to produce a first product system, wherein M represents the mole amount of the II-VI family quantum dot seed crystals, and S2, adding a VI family precursor into the first product system at time intervals at a first rate so that the VI family precursor undergoes a reaction in the first product system at a temperature of 200-300 DEG C to produce a II-VI family quantum dot-containing system, wherein the first rate in a range of 0.1-20M/h and after a full reaction of the VI family precursor, the later VI family precursor is added into the reaction system. The preparation method can produce monodisperse quantum dots with uniform sizes, can be realized easily and is suitable for large scale production.
Description
Technical field
The present invention relates to quanta point material preparation field, in particular to the preparation method of a kind of single dispersing II-VI group quantum dot.
Background technology
Quantum dot is a kind of nanocrystalline, the most only 2～10nm, and luminescent spectrum is with size adjustable.At present be applied to display,
Illumination, solar energy, the numerous areas such as false proof.Size unicity (each quantum dot size phase in a pile quantum dot of quantum dot
With) and the performance of half-peak breadth be highly important for quantum dot application.To unicity height and half-peak width in prior art
The synthesis strategy of quantum dot can be divided three classes, the side that the fast nucleation of class Shi Pengxiaogang seminar exploitation the most slowly grows
Method, along with the carrying out in response time, particle diameter distribution can become narrow gradually；Equations of The Second Kind is to rely on the nanocrystalline of high concentration, relatively small
Nanocrystalline rapid solution, relatively large nanocrystalline slow growth；3rd class is to merge in the solution at primary granule, in granule
Growth generally can make the nanocrystal surface of fusion smooth, and reaches the most single nanocrystal.Three of the above method all exists
A serious drawback is exactly, the most harsh owing to the condition of reaction system is controlled requirement, is not therefore suitable for mass
Produce.
In addition, the synthetic method of prior art, owing to cannot effectively synthesize single dispersing (quasi-magic) quantum dot, is therefore led
Quantum dot entirety half-peak breadth obtained by cause is wider.Such as, the Bawendi of MIT shows at the article of nature in 2013, amount
The half-peak breadth (about between 25～30nm) of son point overall (being interpreted as a pile quantum dot) is more than the half-peak breadth of single quantum dot about
More than 40%.Single dispersing (quasi-magic) quantum dot has the structure determined, extra small particle diameter and the group being accurate to atom due to it
Become and show the physico-chemical property and the optical property that are different from regular quantum point.
Summary of the invention
Present invention is primarily targeted at the preparation method that a kind of single dispersing II-VI group quantum dot is provided, to solve prior art is measured
The problem that son point synthetic method cannot synthesize single dispersing II-VI group quantum dot in high volume.
To achieve these goals, according to an aspect of the invention, it is provided the preparation side of a kind of single dispersing II-VI group quantum dot
Method, including step S1, adds fatty acid in the system containing II-VI group quantum dot crystal seed, make II-VI group quantum dot crystal seed with
Fatty acid is hybrid reaction under conditions of reaction temperature is 200～300 DEG C, obtains the first product system, wherein II-VI group quantum dot
The amount of the material of crystal seed is M；Step S2, is spaced addition VI race precursor in the first product system with First Speed, makes VI race
Precursor in 200～300 DEG C of reactions, obtains the system containing II-VI group quantum dot, wherein, First Speed in the first product system
For 0.1M～20M/h, interval be incorporated as the front VI race precursors reaction once added completely after carry out again on VI race precursor once
Addition.
Further, the molar ratio of above-mentioned fatty acid and II-VI group quantum dot crystal seed is 2:1～200:1.
Further, above-mentioned reaction temperature is 240～280 DEG C.
Further, after above-mentioned steps S2, above-mentioned preparation method also includes: step S3, by containing II-VI group quantum dot
System is warming up to 280 DEG C～320 DEG C and carries out continuing reaction, obtains spherical II-VI group quantum dot.
Further, between above-mentioned steps S2 and step S3, above-mentioned preparation method also includes removing containing II-VI group quantum dot
System in the process of unnecessary II race elemental precursors.
Further, after above-mentioned steps S2, above-mentioned preparation method also includes: carry out the system containing II-VI group quantum dot
Purify, obtain the II-VI group quantum dot of purification；The II-VI group quantum dot of purification is dissolved in non-coordinating solvent, obtains first
Mixed system；First mixed system is heated to 280～320 DEG C to react, obtain spherical II-VI group quantum dot.
Further, after above-mentioned steps S2, above-mentioned preparation method also includes: carry out the system containing II-VI group quantum dot
Purify, obtain the II-VI group quantum dot of purification；The II-VI group quantum dot of purification is dissolved in the mixed of non-coordinating solvent and fatty amine
Close in solution, obtain the second mixed system；Second mixed system is heated to 200～320 DEG C to react, obtain spherical II-VI
Race's quantum dot.
Further, by the above-mentioned system containing II-VI group quantum dot as in step S1 containing II-VI group quantum dot crystal seed
System, or purified the II-VI group quantum dot obtained as the II-VI group in step S1 by the system containing II-VI group quantum dot
Quantum dot crystal seed.
Further, above-mentioned preparation method also includes: II-VI group quantum dot or spherical II-VI group quantum dot after purifying divide
Dissipate formation the 3rd mixed system in non-coordinating solvent；After 3rd mixed system is heated to 200～300 DEG C, to the 3rd mixed system
Middle addition II race elemental precursors, fatty acid and VI race elemental precursors, reaction generates nucleocapsid II-VI group quantum dot.
Application technical scheme, by controlling reaction temperature between 200～300 DEG C, controlling the addition of VI race precursor
Speed can efficiently control the speed of growth of crystal seed, thus obtains the more uniform single dispersing quantum dot of size.And above-mentioned system
The control of the condition of Preparation Method is easier to realize, and is therefore applicable to the large-scale production of II-VI group quantum dot.Interval adds
VI race precursor makes II-VI group quantum dot size become big, and the number of times that interval adds is determined by the target size of II-VI group quantum dot.As
The most not spaced addition, can affect the monodispersity of quantum dot.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows that the application obtains the scanning electron microscope (SEM) photograph of quantum dot crystal seed；
Fig. 2 shows the scanning electron microscope (SEM) photograph of the quantum dot that the embodiment of the present application 1 obtains；And
Fig. 3 shows the scanning electron microscope (SEM) photograph of the monodisperse spherical quantum dot that the embodiment of the present application 17 obtains.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.
Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
As described in background technology, several can synthesize that unicity is high and the quantum dot of half-peak width although prior art has,
But, owing to the condition control of reaction system requires the most harsh, cause these methods to cannot be used for mass production single dispersing
Quantum dot, in order to solve this problem, this application provides the preparation method of a kind of single dispersing II-VI group quantum dot.II-VI therein
The II race element of race's quantum dot is Zn, Cd, Mg, Hg or Pb, and VI race element is S, Se or Te.
Following preparation method if no special instructions, all with to prepare quantum dot in prior art identical to the requirement of reaction environment, instead
The air atmosphere the most all using inert gas atmosphere or wherein dry-off moisture and oxygen before should remove the dampness in reactor and oxygen,
Noble gas therein is nitrogen, argon or rare gas.
In a kind of typical embodiment of the application, this preparation method includes: step S1, to containing II-VI group quantum dot crystal seed
System adds fatty acid, makes II-VI group quantum dot crystal seed mix under conditions of reaction temperature is 200～300 DEG C instead with fatty acid
Should, obtain the first product system, wherein the amount of the material of II-VI group quantum dot crystal seed is M；Step S2, with First Speed to
In first product system, interval adds VI race precursor, makes VI race precursor in 200～300 DEG C of reactions in the first product system, obtains
Containing the system of II-VI group quantum dot, wherein, First Speed is 0.1M～20M/h, and interval is incorporated as once adding front
VI race precursors reaction completely after carry out the addition of VI race precursor next time again.
Above-mentioned preparation method, by reaction temperature being controlled between 200～300 DEG C, the addition speed that controls VI race precursor permissible
Efficiently control the speed of growth of crystal seed, thus obtain the more uniform single dispersing quantum dot of size.And above-mentioned preparation method
The control of condition is easier to realize, and is therefore applicable to the large-scale production of II-VI group quantum dot.Interval adds VI race precursor
Making II-VI group quantum dot size become big, the number of times that interval adds is determined by the target size of II-VI group quantum dot.If it is not spaced
Add, the monodispersity of quantum dot can be affected.
In the implementation process of such scheme, in order to reduce obtained quantum point grain diameter distribution further, the most above-mentioned instead
Answering temperature is 240～280 DEG C.
The II-VI group quantum dot crystal seed of the application can use the preparation method of prior art to prepare, such as following two mode:
Mode one includes: by II race element oxide, fatty acid and non-coordinating solvent, adds the reaction of VI elemental precursors and obtains, side
Formula two includes: II race element soap and non-coordinating solvent are mixed, and adds the reaction of VI elemental precursors and obtains.Through above-mentioned instead
The system that should obtain can be directly as the above-mentioned system containing II-VI group quantum dot crystal seed, it is also possible to will obtain through above-mentioned reaction
System through the isolated and purified crystal seed obtaining the above-mentioned II-VI group quantum dot of crystal seed, and after isolated and purified, add II elemental precursors
Form the system containing II-VI group quantum dot crystal seed.
The speed of seed surface growth is relevant to the degree of passivation of crystal seed with fatty acid, and fatty acid can be passivated seed surface, and suppression adds
The VI race element entered is with the new crystal seed of the II race Element generation in system, and makes the VI race element added uniform at seed surface
Growth.In order to realize the effective control to seeded growth speed, the molar ratio of preferred fatty acid and II-VI group quantum dot crystal seed is
2:1～200:1.Aforementioned proportion can promote II race elemental precursors grow on existing seed surface rather than synthesize new crystal seed,
Synthesize new crystal seed and can affect single dispersing effect.
Use the II-VI group quantum dot that above-mentioned preparation method obtains is shaped as hexahedron, and the quantum dot utilizing this hexahedron is permissible
Prepare monodisperse spherical II-VI group quantum dot and single dispersing nucleocapsid II-VI group quantum dot further.It should be noted that the application
In the shape of quantum dot and not only include regular spherical and hexahedron, also include the spherical or hexahedron of approximation.
Wherein preparing monodisperse spherical II-VI group quantum dot method can be to use following three kinds of modes:
First kind of way is: after step S2, and above-mentioned preparation method also includes: step S3, by containing II-VI group quantum dot
System is warming up to 280 DEG C～320 DEG C and carries out continuing reaction, obtains spherical II-VI group quantum dot.Step S2 and step S3 it
Between, remove and can accelerate conversion speed containing the unnecessary II race elemental precursors in the system of II-VI group quantum dot.
The second way is: after step S2, and above-mentioned preparation method also includes: carry out the system containing II-VI group quantum dot
Purify, obtain the II-VI group quantum dot of purification；The II-VI group quantum dot of purification is dissolved in non-coordinating solvent, obtains first
Mixed system；First mixed system is heated to 200～350 DEG C to react, obtain spherical II-VI group quantum dot.
The third mode is: after step S2, preparation method also includes: purify the system containing II-VI group quantum dot,
Obtain the II-VI group quantum dot of purification；II-VI group quantum dot by purification is dissolved in the mixed solution of non-coordinating solvent and fatty amine
In, obtain the second mixed system；Second mixed system is heated to 200～350 DEG C to react, obtain spherical II-VI group
Quantum dot.
The hexahedron II-VI group quantum dot of step S1 synthesis, by the atomic migration in core, is eliminated by above-mentioned three kinds of modes
Sharp-pointed angle and edge, and then obtained spherical monodisperse nano-particle II-VI group quantum dot.Wherein, the second way is with II-VI after purification
Race's quantum dot is that spherical II-VI group quantum dot prepared by raw material, can accelerate the transformation of shape；The third mode adds fatty amine,
The transformation of shape can be further speeded up.Because the single dispersing quantum dot of smaller size smaller can slowly be converted into spherical quantum dot；Warp
Cross purification to remove freely after part, can greatly accelerate this transformation process.For different size of hexahedron II-VI
Race's quantum dot, the conversion speed of three kinds of modes is different, but can reach identical single dispersing effect.Such as volume relatively
Big single dispersing quantum dot, can add fatty amine and promote conversion, because when improving temperature, fatty amine can replace crystal
The Carboxylic acid ligand on surface, the most at room temperature the fatty amine kinetics of quantum dot surface remains active.Above-mentioned fatty amine is permissible
It is oleyl amine, 18-amine..
The preparation of single dispersing nucleocapsid II-VI group quantum dot can use usual manner of the prior art, and the most above-mentioned preparation method is also
Including: II-VI group quantum dot or spherical II-VI group quantum dot after purifying are scattered in non-coordinating solvent formation the 3rd mixing
System；After 3rd mixed system is heated to 200～300 DEG C, add in the 3rd mixed system II race elemental precursors, fatty acid and
VI race elemental precursors, reaction generates nucleocapsid II-VI group quantum dot.Obtained nucleocapsid II-VI group quantum dot maintains II-VI group
The single dispersing characteristic of quantum dot.
In course of industrialization, in order to improve production efficiency, preferably by the system containing II-VI group quantum dot as in step S1
The system containing II-VI group quantum dot crystal seed, or purified, by the system containing II-VI group quantum dot, the II-VI group quantum that obtains
Point is as the II-VI group quantum dot crystal seed in step S1.
Fatty acid in above-mentioned implementation process can use and synthesize the fatty acid that quantum dot is conventional in prior art, such as oleic acid, ten
Tetracid, stearic acid, the fatty acid of preferably C chain length >=8.Above-mentioned VI race precursor all can use the precursor that prior art is conventional,
Such as Se, S, Te.
Below with reference to embodiment and comparative example, further illustrate the beneficial effect of the application.
The preparation of the crystal seed of all examples below and comparative example 1 is prepared the most as follows:
The synthesis of tetradecylic acid cadmium:
1) in the flask of a 50ml, put into the cadmium acetate of 10mmol and the methanol of 20ml, stir 10 minutes, to cadmium acetate
It is completely dissolved, obtains the methanol solution of cadmium acetate；2) in the flask of another 500ml, by 20mmol tetradecylic acid and 20mmol
Tetramethylammonium hydroxide (TMAH) is dissolved in 100ml methanol, and magnetic agitation is clarified to solution, obtained tetradecylic acid and four for 20 minutes
The methanol solution of ammonium hydroxide；3) methanol solution of the cadmium acetate prepared is slowly added dropwise to tetradecylic acid and tetramethyl hydrogen-oxygen
Change in the methanol solution of ammonium, generate tetradecylic acid cadmium white precipitate；4) continuing stirring reaction 20 minutes, precipitation sucking filtration separates, and uses
Methanol cleans three times and obtains tetradecylic acid cadmium, and the tetradecylic acid cadmium dried in vacuum overnight of gained is standby.
The preparation of Se the first precursor: 0.0120g, i.e. 0.15mmol selenium powder is dispersed in 3ml octadecylene (ODE), and ultrasonic 5
Minute；
The preparation of Se the second precursor: 0.024g, i.e. 0.3mmol selenium powder is dispersed in 3ml ODE, ultrasonic 5 minutes.
The preparation of Cd precursor: by 0.1280g, i.e. 1mmol Aska-Rid. (CdO), 0.5g tetradecylic acid and 4ml ODE put into
Equipped with magneton 25ml three-neck flask obtains mixture, nitrogen bubble aerofluxus 10 minutes in mixture, then mixture is heated up
Obtain colourless solution to 290 DEG C, obtain Cd precursor.
Cd precursor is cooled to 250 DEG C subsequently, is rapidly injected 1ml Se the first precursor wherein and obtains mixed system, by mixed system
Temperature drop to 220 DEG C and continue reaction 10 minutes, obtain the system of CdSe crystal seed containing 0.01mmol, wherein CdSe is brilliant
The ultraviolet absorption peak planted is in 510～520nm scopes.
Embodiment 1
The synthesis of single dispersing CdSe quantum dot:
1.5mmol oleic acid is joined in above-mentioned crystal seed system, stir 5 minutes；Subsequently, reaction temperature is warming up to 250 DEG C,
To the first product system；
Subsequently, take 0.1ml Se the second precursor with sealing injection device, be added dropwise to the first product system with 0.05mmol/h speed, drip
Add follow-up continuous reaction 10 minutes；Reaction temperature is constant at 250 DEG C；Before adding 0.1ml Se second 5 times with this speed loop
Body, every time reaction 10 minutes, i.e. 10 minutes, interval.When CdSe ultraviolet the first absworption peak position reaches 560nm, by whole
Individual reaction system is cooled to room temperature and terminates reaction, obtains the system containing CdSe quantum dot.
Embodiment 2
Other conditions are with embodiment 1, and reaction temperature changes 200 DEG C into, after the circulation of Se the second precursor drips 5 times, and CdSe ultraviolet
First absworption peak position is 535nm.
Embodiment 3
Other conditions are with embodiment 1, and reaction temperature changes 300 DEG C into, after the circulation of Se the second precursor drips 5 times, and CdSe ultraviolet
First absworption peak position is 575nm.
Embodiment 4
Other conditions are with embodiment 1, and reaction temperature is 240 DEG C, after Se the second precursor circulation dropping 5 times, and CdSe ultraviolet the
One absworption peak position is 555nm.
Embodiment 5
Other conditions are with embodiment 1, and reaction temperature changes 280 DEG C into, after the circulation of Se the second precursor drips 5 times, and CdSe ultraviolet
First absworption peak position is 570nm.
Embodiment 6
Other conditions with embodiment 1, the injection rate of Se the second precursor change into 0.001mmol/h, Se second precursor circulation drip
After adding 5 times, CdSe ultraviolet the first absworption peak position is 568nm.
Embodiment 7
Other conditions with embodiment 1, the injection rate of Se the second precursor change into 0.01mmol/h, Se second precursor circulation dropping
After 5 times, CdSe ultraviolet the first absworption peak position is 563nm.
Embodiment 8
Other conditions with embodiment 1, the injection rate of Se the second precursor change into 0.1mmol/h, Se second precursor circulation dropping 5
After secondary, CdSe ultraviolet the first absworption peak position is 557nm.
Embodiment 9
Other conditions with embodiment 1, the injection rate of Se the second precursor change into 0.2mmol/h, Se second precursor circulation dropping 5
After secondary, CdSe ultraviolet the first absworption peak position is 555nm.
Embodiment 10
Other conditions with embodiment 1, the addition of oleic acid change into 0.02mmol, Se second precursor circulation dropping 5 times after,
CdSe ultraviolet the first absworption peak position is 560nm.
Embodiment 11
Other conditions with embodiment 1, the addition of oleic acid change into 0.5mmol, Se second precursor circulation dropping 5 times after, CdSe
Ultraviolet the first absworption peak position is 560nm.
Embodiment 12
Other conditions with embodiment 1, the addition of oleic acid change into 1mmol, Se second precursor circulation dropping 5 times after, CdSe
Ultraviolet the first absworption peak position is 560nm.
Embodiment 13
Other conditions with embodiment 1, the addition of oleic acid change into 2mmol, Se second precursor circulation dropping 5 times after, CdSe
Ultraviolet the first absworption peak position is 560nm.
Embodiment 14
Other conditions are with embodiment 1, and after the circulation of Se the second precursor drips 15 times, CdSe ultraviolet the first absworption peak position is
620nm。
Embodiment 15
Other conditions are with embodiment 1, and after the circulation of Se the second precursor drips 30 times, CdSe ultraviolet the first absworption peak position is
670nm。
Embodiment 16
Other conditions are with embodiment 1, and after the circulation of Se the second precursor drips 30 times, CdSe ultraviolet the first absworption peak position is
685nm。
Embodiment 17
The synthesis of monodisperse spherical CdSe quantum dot:
Prepare scheme according to embodiment 1, after the 5th Se the second precursor drips and reacts 10min, reaction system is warming up to
280 DEG C, react 20min, obtain the monodisperse spherical CdSe quantum dot that ultraviolet the first absworption peak position is 565nm.
Embodiment 18
The synthesis of monodisperse spherical CdSe quantum dot:
Prepare scheme according to embodiment 1, after the 5th Se the second precursor drips and reacts 10min, reaction system is warming up to
320 DEG C, react 20min, obtain the monodisperse spherical CdSe quantum dot that ultraviolet the first absworption peak position is 566nm.
Embodiment 19
The synthesis of monodisperse spherical CdSe quantum dot
After preparing single dispersing CdSe quantum dot according to embodiment 1 method, elder generation is the most isolated and purified:
System containing CdSe quantum dot is positioned over 15ml centrifuge tube, in centrifuge tube, adds acetone, chloroform and methanol (body
Long-pending ratio 1:1:1, altogether 6ml), centrifuge tube is positioned over 4900rpm in centrifuge and is centrifuged 2 minutes.Discard upper liquid, obtain
Quantum dot precipitates, and by quantum dot resolution of precipitate in about 1ml toluene, forms redissolution system, adds in redissolution system the most again
Acetone, chloroform, methanol (volume ratio 1:1:1, altogether 6ml) precipitate and centrifugation again, obtain the single dispersing of purification
CdSe quantum dot.
The single dispersing CdSe quantum dot that purification is good is scattered in the ODE solution of 0.5ml, and is injected into the ODE of 5ml 200 DEG C
In obtain the first mixed system, the first mixed system is warming up to 280 DEG C reaction 20min, obtaining ultraviolet the first absworption peak position is
The monodisperse spherical CdSe quantum dot of 565nm.
Embodiment 20
The synthesis of monodisperse spherical CdSe quantum dot
Prepare according to embodiment 19, reaction temperature is set as 320 DEG C, obtain the list that ultraviolet the first absworption peak position is 565nm
Dispersing ball CdSe quantum dot.
Embodiment 21
The synthesis of monodisperse spherical CdSe quantum dot:
After preparing single dispersing CdSe quantum dot according to embodiment 1 method, elder generation is the most isolated and purified:
To be to be positioned over 15ml centrifuge tube containing CdSe quantum dot, in centrifuge tube, add acetone, chloroform and methanol (volume
Ratio 1:1:1, altogether 6ml), centrifuge tube is positioned over 4900rpm in centrifuge and is centrifuged 2 minutes.Discard upper liquid, the amount of obtaining
Son point precipitation, by quantum dot resolution of precipitate in about 1ml toluene, forms redissolution system, adds third the most again in redissolution system
Ketone, chloroform, methanol (volume ratio 1:1:1, altogether 6ml) precipitate and centrifugation again, obtain single dispersing CdSe amount
Sub-point.
The single dispersing CdSe quantum dot that purification is good is scattered in the ODE solution of 0.5ml, and is injected into the ODE of 5ml 200 DEG C
With oleyl amine (NH2Ol) (mol ratio 1:1) obtains the second mixed system, sets the reaction temperature of the second mixed system as 200 DEG C,
Reaction 20min, obtains the monodisperse spherical CdSe quantum dot that ultraviolet the first absworption peak position is 564nm.
Embodiment 22
The synthesis of monodisperse spherical CdSe quantum dot:
Reaction temperature, with embodiment 21, is set as 280 DEG C by other conditions, and obtaining ultraviolet the first absworption peak position is 565nm
Monodisperse spherical CdSe quantum dot.
Embodiment 23
The synthesis of monodisperse spherical CdSe quantum dot:
Reaction temperature, with embodiment 21, is set as 320 DEG C by other conditions, and obtaining ultraviolet the first absworption peak position is 566nm
Monodisperse spherical CdSe quantum dot.
Embodiment 24
The synthesis of CdSe/CdS nucleocapsid single dispersing quantum dot:
After preparing single dispersing CdSe quantum dot according to embodiment 1 method, elder generation is the most isolated and purified:
System containing CdSe quantum dot is positioned over 15ml centrifuge tube, in centrifuge tube, adds acetone, chloroform and methanol (body
Long-pending ratio 1:1:1, altogether 6ml), centrifuge tube is positioned over 4900rpm in centrifuge and is centrifuged 2 minutes.Discard upper liquid, obtain
Quantum dot precipitates, and by quantum dot resolution of precipitate in about 1ml toluene, forms redissolution system, adds in redissolution system the most again
Acetone, chloroform, methanol (volume ratio 1:1:1, altogether 6ml) precipitate and centrifugation again, obtain single dispersing CdSe
Quantum dot.
The single dispersing CdSe quantum dot that purification is good be scattered in 0.5ml ODE solution (ultraviolet the first absworption peak at 560nm,
OD=10) and the tetradecylic acid cadmium of 0.8mmol joins (cumulative volume is 5ml) in ODE, under agitation, nitrogen bubble 10 points
Clock；Then, 1.5mmol oleic acid is dripped after reaction system being warming up to 250 DEG C wherein；After 1 minute, continue dropping
The ODE solution (0.1mmol/ml) of 0.1ml sulfur, reacts 18 minutes (including time for adding), obtains single dispersing CdSe/CdS
Core-shell quanta dots.
Comparative example 1
In addition to following condition, with embodiment 1
In the system that crystal seed prepares, under the conditions of not adding oleic acid, starting to drip Se the second precursor, the circulation of Se the second precursor is dripped
Adding 5 secondary responses, obtaining ultraviolet the first absworption peak position is 560nm CdSe quantum dot.
Comparative example 2
In addition to following condition, with embodiment 1
In the system not having crystal seed, 1.5mmol oleic acid is joined in above-mentioned system, stir 5 minutes；Subsequently, reaction temperature liter
Temperature is to 250 DEG C；Subsequently, take 0.1ml Se the second precursor with sealing injection device, be added dropwise to 0.05mmol/h speed, be added dropwise to complete
Rear continuation reacts 10 minutes.Se the second precursor circulation dropping 5 secondary responses, obtaining ultraviolet the first absworption peak position is 540nm CdSe
Quantum dot.
Single dispersing quantum dot, monodisperse spherical CdSe quantum dot and the CdSe/CdS nucleocapsid that the various embodiments described above and comparative example obtain
Single dispersing quantum dot is adopted and is detected with the following method:
Use fluorescence spectrophotometer test half-peak breadth and VISIBLE LIGHT EMISSION peak, use ultraviolet-visual spectrometer detection ultraviolet the first absworption peak, inspection
Survey the results are shown in Table 1；Use transmission electron microscope detection size and shape, wherein the detection knot of crystal seed, embodiment 1 and embodiment 17
Fruit sees Fig. 1 to 3.Wherein, half-peak breadth is the important parameter of the monodispersity embodying quantum dot, and monodispersity is the best, half-peak numerical value
The narrowest.
Table 1
By the data in table 1 it can be seen that use the application method to obtain single dispersing quantum dot regular shape, and half-peak breadth is narrower,
Instruction sheet dispersibility is the best.And be can be seen that quantum dot is by crystal seed to hexahedron and spherical transformation by Fig. 1 to 3.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, etc.
With replacement, improvement etc., should be included within the scope of the present invention.
Claims (9)
1. the preparation method of a single dispersing II-VI group quantum dot, it is characterised in that including:
Step S1, adds fatty acid in the system containing II-VI group quantum dot crystal seed, makes described II-VI group quantum dot crystal seed
With described fatty acid hybrid reaction under conditions of reaction temperature is 200～300 DEG C, obtain the first product system, wherein said
The amount of the material of II-VI group quantum dot crystal seed is M；
Step S2, is spaced addition VI race precursor in described first product system with First Speed, makes described VI race precursor
In 200～300 DEG C of reactions in described first product system, obtain the system containing described II-VI group quantum dot, wherein,
Described First Speed is 0.1M～20M/h, described interval be incorporated as the front VI race precursors reaction once added completely after again
Carry out the addition of VI race precursor next time.
Preparation method the most according to claim 1, it is characterised in that described fatty acid and II-VI group quantum dot crystal seed mole
Ratio is 2:1～200:1.
Preparation method the most according to claim 1, it is characterised in that described reaction temperature is 240～280 DEG C.
Preparation method the most according to claim 1, it is characterised in that after described step S2, described preparation method also includes:
Step S3, is warming up to the described system containing II-VI group quantum dot 280 DEG C～320 DEG C and carries out continuing reaction, obtain spherical
II-VI group quantum dot.
Preparation method the most according to claim 4, it is characterised in that between described step S2 and described step S3, institute
State preparation method and also include removing the process of the unnecessary II race elemental precursors in the described system containing II-VI group quantum dot.
Preparation method the most according to claim 1, it is characterised in that after described step S2, described preparation method also includes:
The described system containing II-VI group quantum dot is purified, obtains the II-VI group quantum dot of purification；
The II-VI group quantum dot of described purification is dissolved in non-coordinating solvent, obtains the first mixed system；
Described first mixed system is heated to 280～320 DEG C to react, obtain spherical II-VI group quantum dot.
Preparation method the most according to claim 1, it is characterised in that after described step S2, described preparation method also includes:
The described system containing II-VI group quantum dot is purified, obtains the II-VI group quantum dot of purification；
The II-VI group quantum dot of described purification is dissolved in the mixed solution of non-coordinating solvent and fatty amine, obtains second and mix
Fit system；
Described second mixed system is heated to 200～320 DEG C to react, obtain spherical II-VI group quantum dot.
Preparation method the most according to claim 1, it is characterised in that by the described system containing II-VI group quantum dot as institute
State the described system containing II-VI group quantum dot crystal seed in step S1, or by the described body containing II-VI group quantum dot
System purifies the II-VI group quantum dot obtained as the described II-VI group quantum dot crystal seed in described step S1.
Preparation method the most according to any one of claim 1 to 8, it is characterised in that described preparation method also includes:
II-VI group quantum dot or spherical II-VI group quantum dot after purifying are scattered in non-coordinating solvent formation the 3rd and mix
Fit system；
After described 3rd mixed system is heated to 200～300 DEG C, before adding II race element in described 3rd mixed system
Body, fatty acid and VI race elemental precursors, reaction generates nucleocapsid II-VI group quantum dot.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629783A (en) * | 2017-08-09 | 2018-01-26 | 浙江大学 | Core-shell quanta dots, its preparation method and its application |
| CN108659817A (en) * | 2018-06-14 | 2018-10-16 | 玻尔兹曼智能科技（苏州）有限公司 | A kind of synthetic method and core-shell quanta dots of core-shell quanta dots |
| CN110506096A (en) * | 2017-04-12 | 2019-11-26 | 浙江大学 | Iii-v quantum dot and preparation method thereof |
| CN115893474A (en) * | 2022-09-05 | 2023-04-04 | 浙江大学 | Weak-confinement semiconductor nanocrystal, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601770A (en) * | 2004-10-26 | 2005-03-30 | 中国科学院长春应用化学研究所 | Cadmium sulfide quantum point synthetized by 2-phase heating process |
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
-
2016
- 2016-05-05 CN CN201610297191.1A patent/CN105967154A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601770A (en) * | 2004-10-26 | 2005-03-30 | 中国科学院长春应用化学研究所 | Cadmium sulfide quantum point synthetized by 2-phase heating process |
| CN103936058A (en) * | 2014-05-07 | 2014-07-23 | 吉林大学 | Method for preparing cadmium sulfide quantum dots |
Non-Patent Citations (1)
| Title |
|---|
| JIANHAI ZHOU ET AL.: "A Two-Step Synthetic Strategy toward Monodisperse Colloidal CdSe and CdSe/CdS Core/Shell Nanocrystals", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110506096A (en) * | 2017-04-12 | 2019-11-26 | 浙江大学 | Iii-v quantum dot and preparation method thereof |
| CN110506096B (en) * | 2017-04-12 | 2023-04-28 | 浙江大学 | III-V group quantum dot and preparation method thereof |
| CN107629783A (en) * | 2017-08-09 | 2018-01-26 | 浙江大学 | Core-shell quanta dots, its preparation method and its application |
| CN107629783B (en) * | 2017-08-09 | 2020-06-12 | 浙江大学 | Core-shell quantum dot, preparation method and application thereof |
| CN108659817A (en) * | 2018-06-14 | 2018-10-16 | 玻尔兹曼智能科技（苏州）有限公司 | A kind of synthetic method and core-shell quanta dots of core-shell quanta dots |
| CN115893474A (en) * | 2022-09-05 | 2023-04-04 | 浙江大学 | Weak-confinement semiconductor nanocrystal, preparation method and application thereof |
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