CN109294585A - A kind of CdZnSeS alloy quantum dot and preparation method thereof - Google Patents
A kind of CdZnSeS alloy quantum dot and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of CdZnSeS alloy quantum dots and preparation method thereof.Wherein, CdZnSeS alloy quantum dot preparation method, comprising the following steps: zinc precursor solution is heated to the first temperature by S1；Anionic pre-cursors are added in zinc precursor solution S2, and reaction obtains the mixed liquor containing small size particles, and anionic pre-cursors are selenium precursor, sulphur precursor or selenium sulphur mixing precursor；S3 is added cadmium precursor into mixed liquor and selenium precursor is reacted when the anionic pre-cursors being added in step S2 are sulphur precursor；When the anionic pre-cursors being added in step S2 are selenium precursor, cadmium precursor is added into mixed liquor and sulphur precursor is reacted；When the anionic pre-cursors being added in step S2 are selenium sulphur mixing precursor, cadmium precursor is added into mixed liquor and is reacted.Using the scale topography monodispersity of CdZnSeS alloy quantum dot made from preparation method of the invention is good, component is uniform, fluorescence quantum yield is high, half-peak breadth is relatively narrow.
Description
Technical field
The present invention relates to technology of quantum dots fields more particularly to a kind of CdZnSeS alloy quantum dot and preparation method thereof.
Background technique
Currently, solution semiconductor of the size within the scope of quantum confinement nanocrystalline (solution quantum dot) is with its unique optics
Property receives extensive pass in the fields such as bio-imaging and label, display, solar battery, light emitting diode, single-photon source
Note.In the fields such as biomarker and imaging, light emitting diode, laser, quantum dot photovoltaic device, quantum dot research has become each
One of hot spot from field.The field of people's daily life, quantum dot are influenced in display (quantum dot backlight TV), illumination etc.
Preliminary practical application has been obtained.
Different from traditional binary quantum dot (such as CdSe, CdS) quantum dot can only be controlled with pattern by sized
Level structure, alloy structure quantum dot, can also be by the ratio in modifying ingredients come quantum point in addition to sized
Level structure, this is conducive to the research of photoelectric device.He'nan University Li Linsong teaches seminar in CdZnSe alloy quantum dot
The blue light core-shell quanta dots obtained after outer cladding ZnS, the efficiency of LED device can achieve 16.2%.Compared to list
The binary quantum dot of one component, the stability and efficiency of alloy quantum dot will be higher, and in other words its defect state is less.
Compared to ternary alloy quantum dot (such as CdZnSe, CdZnS), quaternary alloy quantum dot CdZnSeS composed structure is more
Add complexity, adjustable band structure is more.Up to the present, the synthesis of traditional CdZnSeS alloy quantum dot is by selenium sulphur
Precursor is injected at high temperature in cadmium zinc precursor, and one reacts, or that cadmium zinc precursor is injected into selenium sulphur precursor at high temperature is molten
In liquid.But with the progress in reaction time, fluorescence half-peak breadth gradually broadens and (is greater than 30nm).
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of CdZnSeS alloy quantum dot and its
Preparation method, the scale topography monodispersity of CdZnSeS alloy quantum dot is good, component is uniform, fluorescence quantum yield is high, partly
Peak width is relatively narrow.
According to an aspect of the present invention, a kind of CdZnSeS alloy quantum dot preparation method is provided, comprising the following steps:
Zinc precursor solution is heated to the first temperature by S1；
Anionic pre-cursors are added in zinc precursor solution S2, and reaction obtains the mixed liquor containing small size particles, above-mentioned yin
Ion precursor is selenium precursor, sulphur precursor or selenium sulphur mixing precursor；
Cadmium is added into above-mentioned mixed liquor when the above-mentioned anionic pre-cursors being added in above-mentioned steps S2 are sulphur precursor in S3
Precursor and selenium precursor are reacted；When the above-mentioned anionic pre-cursors being added in above-mentioned steps S2 are selenium precursor, to above-mentioned mixing
Cadmium precursor is added in liquid and sulphur precursor is reacted；Before the above-mentioned anionic pre-cursors being added in above-mentioned steps S2 are the mixing of selenium sulphur
When body, cadmium precursor is added into above-mentioned mixed liquor and is reacted.
Further, above-mentioned first temperature is 250~310 DEG C.
Further, the diameter of above-mentioned small size particles is 0.1~3nm, it is preferable that a diameter of 0.5~2nm.
Further, the zinc ion in anion and above-mentioned zinc precursor in above-mentioned steps S2, in above-mentioned anionic pre-cursors
The ratio between the amount of substance be 1:6~1:1.
Further, the zinc ion in cadmium ion and above-mentioned zinc precursor in above-mentioned steps S2 and S3, in above-mentioned cadmium precursor
The ratio between the amount of substance be 1:400~1:10.
Further, in above-mentioned steps S2 and S3, the ratio between selenium element and the amount of substance of element sulphur of addition are 1:7~7:
1。
It is above-mentioned that further in above-mentioned steps S2, above-mentioned zinc precursor is selected from the zinc polycarboxylate that carbon chain lengths are 8~22,
In above-mentioned steps S3, above-mentioned cadmium precursor is selected from the carboxylic acid cadmium that carbon chain lengths are 1~22.
A preferred embodiment of first aspect according to the present invention in above-mentioned steps S3, is added when in above-mentioned steps S2
Above-mentioned anionic pre-cursors when being sulphur precursor, cadmium precursor is first added into above-mentioned mixed liquor, then add selenium precursor carry out it is anti-
It answers, or selenium precursor is first added into above-mentioned mixed liquor, then add cadmium precursor and reacted.
Another preferred embodiment of first aspect according to the present invention, in above-mentioned steps S3, when in above-mentioned steps S2 plus
When the above-mentioned anionic pre-cursors entered are selenium precursor, cadmium precursor is first added into above-mentioned mixed liquor, then adds the progress of sulphur precursor
Reaction, or sulphur precursor is first added into above-mentioned mixed liquor, it then adds cadmium precursor and is reacted.
Another preferred embodiment of first aspect according to the present invention, in above-mentioned steps S3, when in above-mentioned steps S2 plus
When the above-mentioned anionic pre-cursors entered are selenium sulphur mixing precursor, after cadmium precursor reaction a period of time is added into above-mentioned mixed liquor, so
One of selenium precursor, sulphur precursor or selenium sulphur mixing precursor or a variety of is added again afterwards.
Further, after above-mentioned cadmium precursor reaction a period of time is added into above-mentioned mixed liquor, selenium is then added several times
The different selenium sulphur mixing precursor of the molar ratio of element sulphur.
According to another aspect of the present invention, a kind of CdZnSeS alloy quantum dot is provided, by above-mentioned preparation side of the invention
Method is made.
Further, the wavelength of fluorescence that above-mentioned CdZnSeS alloy quantum dot issues is between 500~570nm, fluorescence half-peak
Width is 18~25nm, and fluorescence quantum yield is greater than 80%.
According to another aspect of the present invention, a kind of CdZnSeS/ZnS core-shell quanta dots are provided, the CdZnSeS/ZnS core
Shell quantum dot passes through the above-mentioned CdZnSeS alloy quantum that will be purified and is added in zinc precursor solution, then adds sulphur precursors reaction
It obtains.
According to another aspect of the present invention, a kind of electronic device is provided comprising above-mentioned CdZnSeS alloy of the invention
Quantum dot.
Compared with prior art, the beneficial effects of the present invention are the preparation sides of CdZnSeS alloy quantum dot of the invention
Method is then added cadmium precursor and carries out cationic exchange, formed containing the small of cadmium using the small size particles for being nucleated initial stage formation as substrate
Then sized particles carry out the growth of quantum dot on this basis, cadmium atom gradually diffuses to entire particle during the growth process,
To obtain, component is uniform, the more complete high-quantum efficiency of alloying, narrow half-peak breadth CdZnSeS alloy quantum dot；The present invention
CdZnSeS alloy quantum dot preparation method, it is possible to reduce the diadactic structures quantum such as CdSe, CdS occurs during the growth process
The self-contained nuclear phenomenon of point；Preparation method of the invention, can also be by adjusting the additional amount of different precursors or the time being added, to adjust
Save the band structure of CdZnSeS alloy quantum dot.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
The present invention provides a kind of CdZnSeS alloy quantum dot preparation method, including following following steps:
Zinc precursor solution is heated to the first temperature by S1；
Anionic pre-cursors are added in above-mentioned zinc precursor solution S2, and reaction obtains the mixed liquor containing small size particles, on
Stating anionic pre-cursors is selenium precursor, sulphur precursor or selenium sulphur mixing precursor；
Cadmium precursor is added into above-mentioned mixed liquor when the anionic pre-cursors being added in above-mentioned steps S2 are sulphur precursor in S3
It is reacted with selenium precursor；When the anionic pre-cursors being added in above-mentioned steps S2 are selenium precursor, it is added into above-mentioned mixed liquor
Cadmium precursor and sulphur precursor are reacted；When the anionic pre-cursors being added in above-mentioned steps S2 are selenium sulphur mixing precursor, to above-mentioned
Cadmium precursor is added in mixed liquor to be reacted.
In step S2, anionic pre-cursors and zinc precursors reaction obtain small size particles, not according to the type of anionic pre-cursors
Together, small size particles can be ZnSe or ZnS or ZnSeS.Small size particles refer to nucleation initial stage ZnSe or ZnS or ZnSeS shape
At the relatively small quantum point of cluster or size, formed small size particles after immediately enter step S3.In some embodiments
In, it is rapidly injected cadmium precursor in step s3, cadmium precursor is by the way that quickly fully cation exchange reaction is diffused into above-mentioned small ruler
In very little particle, in addition, the selenium precursor or sulphur precursor that are added in step S3 also assist in the growth course of quantum dot, to obtain
CdZnSeS alloy quantum dot.In further embodiments, in step s3, by changing the addition time of cadmium precursor, realization changes
Become the peak position of alloy quantum dot；And under the premise of the additional amount of guarantee cadmium precursor is identical, the longer peak of time interval is added
Position is smaller.
The present invention is initially formed the small size particles without cadmium, favorably in the growth course of CdZnSeS alloy quantum dot
In control small size particles pattern, the homogeneity of component, then adds cadmium precursor and carry out cationic exchange, then make cadmium atom
Entire quantum dot is gradually diffused to during continuing cladding in ZnSeS, finally obtains that scale topography is uniform, component is uniform
CdZnSeS quantum dot.In entire growth course the self-contained of CdSe, CdS diadactic structure quantum dot will not occur substantially for this method
Nuclear phenomenon, therefore be conducive to obtain the CdZnSeS alloy quantum dot that scale topography is uniform, component is uniform.In addition, the present invention passes through
The interval time of regulating step S3 and step S2, the band structure of adjustable CdZnSeS alloy quantum dot.
In some embodiments, above-mentioned first temperature is 250~310 DEG C, i.e., first heats zinc precursor solution, then exist
Selenium precursor, sulphur precursor or selenium sulphur mixing precursor are added under high temperature, to form the small size particles for being free of cadmium, is conducive to control small
The homogeneity of sized particles pattern, component.
In some embodiments, the width of above-mentioned small size particles is 0.1~3nm.Small size particles described in the present invention
Not necessarily sphere is also possible to cluster, and the width of small size particles refers to herein: a face of small size particles three-dimensional structure
Maximum width when by micro- sem observation.
Preferably, the width of above-mentioned small size particles is 0.5~2nm.
In some embodiments, zinc precursor is selected from the zinc polycarboxylate that carbon chain lengths are 8~22.It is noted that in this hair
In bright, zinc precursor can be the zinc polycarboxylate prepared in advance, be also possible to before the reaction of step S1 carries out, the shape in solution
At zinc polycarboxylate, for example, basic zinc carbonate and oleic acid are mixed in solution, after reaction zinc precursor solution.Cadmium precursor is selected from
The carboxylic acid cadmium that carbon chain lengths are 1~22.
Sulphur precursor, the type of selenium precursor and selenium sulphur mixing precursor and preparation method belong to the state of the art,
And will not be described here in detail.
In some embodiments, in step S2, the substance of the zinc ion in anion and zinc precursor in anionic pre-cursors
The ratio between amount be 1:6~1:1.
In some embodiments, in step S2 and S3, the substance of the zinc ion in cadmium ion and zinc precursor in cadmium precursor
The ratio between amount be 1:400~1:10.Cadmium ion and zinc ion described herein refer to: in whole preparation process, the cadmium of addition
Ion and zinc ion.
In some embodiments, in step S2 and S3, the ratio between amount of substance of selenium element of addition and element sulphur for 1:7~
7:1.Selenium element described herein refers to element sulphur: in whole preparation process, the selenium element and element sulphur of addition.
In some embodiments, in step s3, when the anionic pre-cursors being added in step S2 are sulphur precursor, first to mixed
It closes in liquid and cadmium precursor is added, then add selenium precursor and reacted, or selenium precursor is first added into the mixed liquor, then
Cadmium precursor is added to be reacted.Namely make cadmium precursor and selenium when continued growth quantum dot on the basis of small size particles ZnS
Precursor is added separately to, and is conducive to the self-contained nuclear phenomenon for being further reduced CdSe binary quantum dot in this way, meanwhile, the cadmium precursor of addition
Carry out cationic exchange with the zinc atom in ZnS, the scale topography monodispersity of the CdZnSeS alloy quantum dot improved with
And the homogeneity of component.
In some embodiments, in step s3, when the anionic pre-cursors being added in step S2 are selenium precursor, first
Cadmium precursor is added into mixed liquor, then adds sulphur precursor and is reacted, or sulphur precursor is first added into mixed liquor, then
Cadmium precursor is added to be reacted.Namely on the basis of small size particles ZnSe when continued growth quantum dot, make cadmium precursor with
Sulphur precursor is added separately to, and is conducive to the self-contained nuclear phenomenon for being further reduced CdS binary quantum dot in this way, meanwhile, before the cadmium of addition
Zinc atom in body and ZnSe carries out cationic exchange, the scale topography monodisperse of the CdZnSeS alloy quantum dot improved
The homogeneity of property and component.
In some embodiments, in step s3, mixed for selenium sulphur when the anionic pre-cursors being added in the step S2
When closing precursor, after cadmium precursor reaction a period of time is added into the mixed liquor, selenium precursor, sulphur precursor or selenium are then added again
One of sulphur mixing precursor is a variety of, or the different selenium sulphur mixing precursor of molar ratio of selenium element sulphur is added several times.?
I.e. on the basis of small size particles ZnSeS when continued growth quantum dot, obtained after cadmium precursor reaction a period of time is first added
Then CdZnSeS cluster further coats ZnSeS by adding selenium precursor, sulphur precursor or selenium sulphur mixing precursor again, and wrapping
Cadmium atom is constantly spread toward shell during covering, to improve the scale topography monodispersity of CdZnSeS alloy quantum dot
And the homogeneity of component, while adjusting the Fluorescent peal of CdZnSeS alloy quantum dot.
The CdZnSeS alloy quantum dot being prepared by the above method of the invention, the wavelength of fluorescence issued 500~
Between 570nm, fluorescence half-peak breadth is 18~25nm, and fluorescence quantum yield is greater than 80%.
In addition, cladding one can be continued after the CdZnSeS alloy quantum dot purification that the above method of the invention is prepared
ZnS shell, to improve the stability of quantum dot.
In the method for CdZnSeS alloy quantum dot outer cladding ZnS shell are as follows: add the CdZnSeS alloy quantum dot of purification
Enter in zinc precursor solution, then adds sulphur precursor and reacted to obtain.
The present invention also provides a kind of electronic devices, including above-mentioned CdZnSeS alloy quantum dot.Above-mentioned electronic device can be electricity
Photoluminescence diode (QLED), Organic Light Emitting Diode (OLED), light emitting diode (LED), various displays are (for example, liquid crystal
Display (LCD)), it is solar battery, sensor, hybrid composition, biomarker or imaging sensor, safety ink, various
Lighting apparatus etc., but not limited to this.
The preparation of precursors:
The preparation of 2mmol/mL S-TOP solution: weighing 0.64g S, places it in the vial of 20mL rubber plug and seals,
Wherein air is discharged with inert gas.Inject 10mL TOP, by this mixture repeatedly oscillating ultrasonic until S sufficiently dissolve.
The preparation of 0.5mmol/mL S-TOP solution: taking 2.5mL 2mmol/mL S-TOP solution, and it is mixed that 7.5mL ODE is added
It closes uniform.
The preparation of 2mmol/mL Se-TOP solution: weighing 1.58g Se, places it in close in the vial of 20mL rubber plug
Envelope injects 10mL TOP with inert gas discharge wherein air, by this mixture repeatedly oscillating ultrasonic until Se sufficiently dissolves.
The preparation of Se-S-TOP solution (Se:S=2.5:1.5): 0.48g S is weighed, 1.97g Se places it in 20mL glue
It is sealed in the vial of plug, wherein air is discharged with inert gas, injects 10mL TOP, oscillating ultrasonic is straight repeatedly by this mixture
It is sufficiently dissolved to Se, S, the configuration of other concentration need to only change the amount of Se, S.
The preparation of 0.2mmol/mL oleic acid cadmium solution: 0.2560g cadmium oxide (CdO), 5mmol oleic acid, 10mL ODE are weighed
In three-neck flask, be passed through inert gas and be vented 10 minutes, increase temperature to 280 DEG C, obtain clear solution, stop reaction to
With.
Quantum dot method of purification: it takes 10mL stoste in 50mL centrifuge tube, 40mL acetone is added, is heated to about 50 DEG C, then
It is precipitated 3 minutes with 8000 revs/min of speed high speed centrifugation, takes out, outwell supernatant.Sediment is dissolved in a certain amount of toluene
In.
[embodiment 1]
The synthesis of CdZnSeS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Then it reduces
Temperature is injected 1mL Se-S-TOP solution (Se:S=2.5:1.5) to 250 DEG C, is then rapidly injected 2mL 0.2mmol/mL oil
Sour cadmium solution increases temperature to 300 DEG C, the reaction was continued 20min, stopping reaction.
[embodiment 2]
The synthesis of CdZnSeS/ZnS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10gODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), be then rapidly injected 2mL 0.2mmol/mL cadmium oleate
Solution increases temperature to 300 DEG C, and the reaction was continued 20 minutes, stops reaction, and near room temperature is purified and is dissolved in 1mL ODE.
Basic zinc carbonate (0.66g, 1.2mmol), 2.8g oleic acid, 5g ODE are weighed in 100mL three-neck flask, uses inertia
Gas exhaust 10 minutes；Temperature is increased to 300 DEG C, obtains clear solution；The CdZnSeS quantum dot purified is injected, with 5mL/h
Speed be added dropwise 10mL 0.5mmol/mL S-TOP solution, after completion of dropwise addition, stop reaction.
[embodiment 3]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
It to 250 DEG C, injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), reacts 1 minute, inject 2mL 0.2mmol/mL oleic acid
Cadmium solution increases temperature to 300 DEG C, and the reaction was continued 20 minutes, stops reaction.
[embodiment 4]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), be then rapidly injected 2mL 0.2mmol/mL cadmium oleate
Solution reacts 1min, injects 0.25mL 2mmol/mL Se-TOP solution, increases temperature to 300 DEG C, and the reaction was continued 20 minutes,
Stop reaction.
[embodiment 5]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), be then rapidly injected 2mL 0.2mmol/mL cadmium oleate
Solution reacts 1min, injects 0.25mL 2mmol/mL S-TOP solution, increases temperature to 300 DEG C, the reaction was continued 20 minutes, stops
Only react.
[embodiment 6]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), be then rapidly injected 2mL 0.2mmol/mL cadmium oleate
Solution, react 1min, inject the same concentration of 0.25mL Se-S-TOP solution, increase temperature to 300 DEG C, the reaction was continued 20 points
Clock stops reaction.
[embodiment 7]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, 1mL 2mmol/mL Se-TOP solution is injected, is then rapidly injected 2mL 0.2mmol/mL oleic acid cadmium solution, then
It is rapidly injected 1mL 2mmol/mL S-TOP solution, increases temperature to 300 DEG C, the reaction was continued 20 minutes, stops reaction.
[embodiment 8]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, 1mL 2mmol/mL S-TOP solution is injected, is then rapidly injected 2mL 0.2mmol/mL oleic acid cadmium solution, then
It is rapidly injected 1mL 2mmol/mL Se-TOP solution, increases temperature to 300 DEG C, the reaction was continued 20 minutes, stops reaction.
[embodiment 9]
The synthesis of CdZnSeS quantum dot: take 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Reduce temperature
To 250 DEG C, 1mL 2mmol/mL Se-TOP solution is injected, 1mL 2mmol/mL S-TOP solution is then rapidly injected, it is then fast
Speed injection 2mL 0.2mmol/mL oleic acid cadmium solution, increases temperature to 300 DEG C, and the reaction was continued 20 minutes, stops reaction.
[embodiment 10]
The synthesis of CdZnSeS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Then it reduces
Temperature is injected 1mL Se-S-TOP solution (Se:S=2.5:1.5) to 250 DEG C, is then rapidly injected 1mL 0.2mmol/mL oil
Sour cadmium solution increases temperature to 300 DEG C, the reaction was continued 20min, stopping reaction.
[embodiment 11]
The synthesis of CdZnSeS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Then it reduces
Temperature is injected 2mL Se-S-TOP solution (Se:S=2.5:1.5) to 250 DEG C, is then rapidly injected 1mL 0.2mmol/mL oil
Sour cadmium solution increases temperature to 300 DEG C, the reaction was continued 20min, stopping reaction.
[embodiment 12]
The synthesis of CdZnSeS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Then it reduces
Temperature is injected 1mL Se-S-TOP solution (Se:S=1.3:2) to 250 DEG C, is then rapidly injected 1mL 0.2mmol/mL oleic acid
Cadmium solution increases temperature to 300 DEG C, the reaction was continued 20min, stopping reaction.
[embodiment 13]
The synthesis of CdZnSeS quantum dot: taking 0.66g basic zinc carbonate (1.2mmol), 4.2g oleic acid, 10g ODE in
It in 100mL three-neck flask, is passed through inert gas and is vented 10 minutes, increase temperature to 300 DEG C, obtain clear solution；Then it reduces
Temperature is injected 0.5mL Se-S-TOP solution (Se:S=3.5:0.5) to 250 DEG C, is then rapidly injected 2mL 0.2mmol/mL
Oleic acid cadmium solution, increase temperature to 300 DEG C, react 5min, re-inject 0.5ml Se-S-TOP solution (Se:S=2.5:
1.5) 5min, is reacted, is re-injected 0.5mlSe-S-TOP solution (Se:S=1.5:2.5), 10min is reacted, stops reaction.
[comparative example 1]
8mmol zinc acetate, 0.2mmol selenium powder, 5.2ml oleic acid and 15ml octadecylene are added to condenser pipe and temperature
In the three-necked flask of meter, 150 DEG C vacuumize 20min, and inflated with nitrogen is heated to 280 DEG C, and 0.1mmol/mL cadmium oleate 1- is then added dropwise
Octadecene solution monitors product fluorescence emission peak wavelength, and when reaching required light emitting peak wavelength, continuing dropwise addition 3ml concentration is
The trioctylamine solution of 4mol/L 1- spicy thioalcohol, control are dripped off in 50min.The reaction was continued at 280 DEG C 30min.It is cooled to room temperature.
[comparative example 2]
0.4mmolCdO is weighed, 4mmol zinc acetate, 17.6mmol oleic acid, 20mL octadecylene is in 100mL three-neck flask.
It at 150 DEG C, is passed through inert gas and is vented 30 minutes, increase temperature to temperature is increased to 300 DEG C, obtain clear solution；Then it rises
High-temperature injects 1mL Se-S-TOP solution (Se:S=2.5:1.5) to 310 DEG C, the reaction was continued 20min, stopping reaction.
[comparative example 3]
0.4mmolCdO is weighed, 4mmol zinc acetate, 17.6mmol oleic acid, 20mL octadecylene is in 100mL three-neck flask.
It at 150 DEG C, is passed through inert gas and is vented 30 minutes, increase temperature to temperature is increased to 300 DEG C, obtain clear solution；Then it rises
High-temperature injects 1mL Se-S-TOP solution (Se:S=2.5:1.5), the reaction was continued 20min to 310 DEG C, stops reaction, mentions
It is pure.
Basic zinc carbonate (0.66g, 1.2mmol), 2.8g oleic acid, 5g ODE are weighed in 100mL three-neck flask, uses inertia
Gas exhaust 10 minutes；Temperature is increased to 300 DEG C, obtains clear solution；The CdZnSeS quantum dot purified is injected, with 5mL/h
Speed be added dropwise 10mL 0.5mmol/mL S-TOP solution, after completion of dropwise addition, stop reaction.
[comparative example 4]
0.8mmolCdO is weighed, 8mmol zinc acetate, 35.2mmol oleic acid, 10mL octadecylene is in 100mL three-neck flask.
It at 150 DEG C, is passed through inert gas and is vented 30 minutes, increase temperature to temperature is increased to 300 DEG C, obtain clear solution, be cooled to
200 DEG C, for use；
Weigh 2.5mmolSe powder, 1.5mmolS powder in 15mL ODE and 100mL three-neck flask, is passed through inert gas exhaust
10 minutes, temperature was increased to 280 DEG C.The above-mentioned cation precursor solution injection of 5mL is taken, 20min is reacted, stops reaction.
The various embodiments described above and the finally obtained quantum dot of comparative example are detected, are tested using fluorescence emission spectrometer
Its emission peak and half-peak breadth survey its fluorescence efficiency using integrating sphere, and testing result is shown in Table 1.
Table 1
From table 1 data of embodiment 1-13 and comparative example 1-4 can be seen that preparation method of the invention obtain it is various
CdZnSeS quantum dot or CdZnSeS/ZnS quantum dot have narrower half-peak breadth and higher fluorescence efficiency.
It is worth noting that, selenium source and zinc source heat up after mixing in comparative example 1 (prior art), obtain first
It is ZnSe nanoparticle, the nano-particles size that this growing method obtains is inhomogenous, and half-peak breadth is wider；Then by slow
Cadmium salt is added dropwise and carries out partial cation exchange, what is obtained is ZnSe/CdZnSe core-shell quanta dots, continues thereafter with and sulphur source is slowly added dropwise
Or the mixed liquor of sulphur source and zinc source, coat ZnS.Therefore the structure that the preparation method of comparative example 1 obtains is actually ZnSe/
CdZnSe/ZnS core-shell quanta dots, rather than CdZnSeS alloy quantum dot.In addition, although being slowly added into cadmium source in comparative example 1
Cationic exchange is carried out, but the quantum dot cadmium atomic component that this exchange result obtains is inhomogenous, it is more on some quantum dots, have
It is few on a little quantum dots, it is possible to which that the quantum dot half-peak breadth for seeing that it is obtained is very wide.And for the angle of energy band, ZnSe's
Energy band will be wider than CdZnSe, be unfavorable for the protection to exciton.
The preparation method of CdZnSeS alloy quantum dot of the invention, using be nucleated initial stage formation small size particles as substrate,
Cadmium precursor is then added and carries out cationic exchange, forms the small size particles containing cadmium, then carries out quantum dot on this basis
Growth, cadmium atom gradually diffuses to entire particle during the growth process, to obtain that component is uniform, alloying is more complete high
Quantum efficiency, narrow half-peak breadth CdZnSeS alloy quantum dot；It, can also be by adjusting different precursors from preparation method of the invention
Additional amount or be added the time, to adjust the band structure of CdZnSeS alloy quantum dot.
In order to further detect the stability of quantum dot of the invention, quantum made from embodiment 2 and comparative example 3 is used respectively
Point prepare quantum dot film, to quantum dot film carry out ageing stability detection, test result (under the conditions of the high light intensity of high temperature, 60 DEG C,
50mA) it is shown in Table 2.
Table 2
| Quantum dot light emitting efficiency (initial) | Quantum dot light emitting efficiency (aging 500h) | |
| Embodiment 2 | 60% | 55% |
| Comparative example 3 | 45% | 36% |
The quantum dot made from the embodiment of the present invention 2 it can be seen from the data in table 2 is after the high light intensity aging 500h of high temperature
Quantum dot light emitting efficiency reduces by 5%, and the quantum dot light emitting after the high light intensity aging 500h of high temperature of quantum dot made from comparative example 3 is imitated
Rate reduces 9%, illustrates the preparation method of CdZnSeS alloy quantum dot of the invention, and obtained alloy quantum dot stability is high,
Application and intrinsic optic Quality Research for alloy quantum dot have great impetus.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (15)
1. a kind of CdZnSeS alloy quantum dot preparation method, which comprises the following steps:
Zinc precursor solution is heated to the first temperature by S1；
Anionic pre-cursors are added in the zinc precursor solution S2, and reaction obtains the mixed liquor containing small size particles, the yin
Ion precursor is selenium precursor, sulphur precursor or selenium sulphur mixing precursor；
Cadmium precursor is added into the mixed liquor when the anionic pre-cursors being added in the step S2 are sulphur precursor in S3
It is reacted with selenium precursor；When the anionic pre-cursors being added in the step S2 are selenium precursor, into the mixed liquor
Cadmium precursor is added and sulphur precursor is reacted；When the anionic pre-cursors being added in the step S2 are selenium sulphur mixing precursor
When, cadmium precursor is added into the mixed liquor and is reacted.
2. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that first temperature is
250~310 DEG C.
3. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the small size particles
Diameter be 0.1~3nm, it is preferable that a diameter of 0.5~2nm.
4. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that in the step S2, institute
The ratio between amount of substance of zinc ion in the anion and the zinc precursor in anionic pre-cursors is stated as 1:6~1:1.
5. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the step S2 and S3
In, the ratio between the amount of substance of zinc ion in cadmium ion and the zinc precursor in the cadmium precursor is 1:400~1:10.
6. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the step S2 and S3
In, the ratio between selenium element and the amount of substance of element sulphur of addition are 1:7~7:1.
7. CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that in the step S2, institute
State zinc precursor and be selected from the zinc polycarboxylate that carbon chain lengths are 8~22, in the step S3, the cadmium precursor be selected from carbon chain lengths be 1~
22 carboxylic acid cadmium.
8. -7 any CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the step
In S3, when the anionic pre-cursors being added in the step S2 are sulphur precursor, cadmium precursor first is added into the mixed liquor,
Then it adds selenium precursor to be reacted, or selenium precursor is first added into the mixed liquor, then add cadmium precursor progress
Reaction.
9. -7 any CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the step
In S3, when the anionic pre-cursors being added in the step S2 are selenium precursor, cadmium precursor first is added into the mixed liquor,
Then it adds sulphur precursor to be reacted, or sulphur precursor is first added into the mixed liquor, then add cadmium precursor progress
Reaction.
10. -7 any CdZnSeS alloy quantum dot preparation method according to claim 1, which is characterized in that the step
In S3, when the anionic pre-cursors being added in the step S2 are selenium sulphur mixing precursor, cadmium is added into the mixed liquor
Precursors reaction for a period of time after, one of selenium precursor, sulphur precursor or selenium sulphur mixing precursor or a variety of are then added again.
11. CdZnSeS alloy quantum dot preparation method according to claim 10, which is characterized in that the mixed liquor
After middle addition described cadmium precursor reaction a period of time, then before the different selenium sulphur mixing of the molar ratio of addition selenium element sulphur several times
Body.
12. a kind of CdZnSeS alloy quantum dot, which is characterized in that the CdZnSeS alloy quantum dot is appointed by claim 1-11
Method described in one is prepared.
13. CdZnSeS alloy quantum dot according to claim 12, which is characterized in that the CdZnSeS alloy quantum dot
For the wavelength of fluorescence of sending between 500~570nm, fluorescence half-peak breadth is 18~25nm, and fluorescence quantum yield is greater than 80%.
14. a kind of CdZnSeS/ZnS core-shell quanta dots, which is characterized in that the CdZnSeS/ZnS core-shell quanta dots will be by that will mention
CdZnSeS alloy quantum dot described in pure claim 12 or 13 be added zinc precursor solution in, then add sulphur precursor into
Row reaction obtains.
15. a kind of electronic device, which is characterized in that the electronic device includes any quantum dot of claim 12-14.
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