CN110129054A - Core-shell quanta dots and preparation method thereof, quantum dot optoelectronic devices - Google Patents
Core-shell quanta dots and preparation method thereof, quantum dot optoelectronic devices Download PDFInfo
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Abstract
The invention discloses core-shell quanta dots and preparation method thereof, quantum dot optoelectronic devices.Wherein the preparation method of core-shell quanta dots mixes the solution comprising quantum dot core with zinc precursor in the reaction vessel the following steps are included: S1, provides quantum dot core；S2, after the completion of step S1, sulphur precursor and transition zone precursor is added to reaction vessel several times, sulphur precursor is not added simultaneously with transition zone precursor, sulphur precursor and zinc precursors reaction generate multiple ZnS layers, transition zone precursor at least generates multiple transition zones with zinc precursors reaction, and wherein the band gap width of transition zone is less than ZnS layers of band gap width, and the single additional amount of control transition zone precursor makes the thickness of transition zone be no more than 1 layer；After the completion of S3, step S2, sulphur precursor is added into reaction vessel, zinc precursor and sulphur precursors reaction generate ZnS layers, the system containing core-shell quanta dots obtained after reaction.
Description
Technical field
The present invention relates to quanta point materials more particularly to core-shell quanta dots and preparation method thereof, quantum dot optoelectronic devices.
Background technique
In past two ten years, quantum dot synthesis chemistry is concentrated mainly on the monodisperse control and such as of scale topography
What is improved on fluorescence quantum yield.But to make quantum dot as a kind of excellent luminous and photoelectric material, it is upper important in synthesis
Target be to reduce environment as far as possible, the especially influence of water and oxygen for properties such as optics, the electricity of quantum dot, this is right
There is great impetus in the science of quantum dot and application study.
Stable quantum dot is obtained, often simplest method is bigger in nuclear quantum dot surface cladding band gap width
Shell Materials, and shell thickness wants thick, to completely cut off the contact between exciton and environment.For example, teacher's Peng Xiaogang class in 2014
Topic group reports after small size CdSe (3nm) quantum dot surface coats 10~16 layers of CdS, has obtained optics and chemical stability
Preferable CdSe/CdS core-shell quanta dots.But quantum dot size is too big, can be answered in the fields such as biomarker and imaging it
With being restricted, and cost is also higher.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of cores that cost is relatively low, stability is good
Shell quantum dot and preparation method thereof.
According to an aspect of the present invention, a kind of preparation method of core-shell quanta dots is provided, comprising the following steps:
S1 provides quantum dot core, and the solution comprising above-mentioned quantum dot core is mixed in the reaction vessel with zinc precursor；
After the completion of S2, above-mentioned steps S1, sulphur precursor and transition zone precursor, above-mentioned sulphur is added to above-mentioned reaction vessel several times
Precursor is not added simultaneously with above-mentioned transition zone precursor, and above-mentioned sulphur precursor and above-mentioned zinc precursors reaction generate multiple ZnS layers, above-mentioned mistake
It crosses layer precursor and at least generates multiple transition zones with above-mentioned zinc precursors reaction, wherein the band gap width of above-mentioned transition zone is less than above-mentioned
ZnS layers of band gap width, the single additional amount for controlling above-mentioned transition zone precursor make the thickness of above-mentioned transition zone be no more than 1 layer；
After the completion of S3, above-mentioned steps S2, sulphur precursor, above-mentioned zinc precursor and above-mentioned sulphur precursor are added in Xiang Shangshu reaction vessel
Reaction generates ZnS layers, and the system containing core-shell quanta dots is obtained after reaction；
In each step, above-mentioned sulphur precursor each type and additional amount is identical or different, and above-mentioned transition zone precursor is each
Type and additional amount it is identical or different.
Further, the above-mentioned quantum dot core of above-mentioned steps S1 be selected from following one kind: CdZnSeS, CdZnSe, CdZnS,
CdSe、CdS、CdSeS、InP。
Further, above-mentioned transition zone precursor includes at least one of above-mentioned quantum dot core anion and/or cation
Precursor, it is preferable that above-mentioned transition zone precursor includes one or more of: cadmium precursor, zinc precursor, selenium precursor, sulphur precursor, phosphorus
Precursor.
Further, in above-mentioned steps S2, the amount of the substance for the above-mentioned sulphur precursor that generation one is added when ZnS layers above-mentioned is denoted as
M1, generate and be denoted as M with the amount of the substance for the above-mentioned transition precursor being added when the above-mentioned ZnS layers of adjacent above-mentioned transition zone2, M1:M2
=(5~100): 1.
According to another aspect of the present invention, a kind of core-shell quanta dots are provided, including quantum dot core and are coated on above-mentioned
The thickness of the outermost ZnS shell of quantum dot core, above-mentioned ZnS shell is greater than 9 layers, and above-mentioned ZnS shell exists radially spacedly
Above-mentioned ZnS shell is divided into ZnS layers multiple, the band gap width of each above-mentioned transition zone by multiple transition zones, multiple above-mentioned transition zones
Less than above-mentioned ZnS layers of band gap width, the thickness of above-mentioned transition zone is no more than 1 layer.
Further, the thickness of above-mentioned ZnS shell is less than or equal to 30 layers.
Further, above-mentioned quantum dot core is selected from CdSe, CdZnSeS, CdZnSe, CdZnS, CdSe, CdS, CdSeS, InP
One of.
Further, the fluorescence efficiency of above-mentioned core-shell quanta dots is greater than 80%.
Further, each above-mentioned transition zone is identical or not identical, and above-mentioned transition zone and above-mentioned quantum dot core have at least one
Identical element, above-mentioned transition zone have at least one identical element with above-mentioned ZnS layers.
According to a further aspect of the invention, a kind of quantum dot optoelectronic devices are provided, including the nucleocapsid above-mentioned by the present invention
The above-mentioned core-shell quanta dots of the quantum dot or the present invention that the preparation method of quantum dot is prepared.
Compared with prior art, the beneficial effects of the present invention are: the present invention quantum dot core outer cladding thickness ZnS shell,
Obtain that optical property is excellent, the good core-shell quanta dots of water resistant oxygen performance；The present invention, which provides core-shell quanta dots preparation method, to be had very
Good universality, is suitable for different types of quantum dot epitaxial growth ZnS shell.
Detailed description of the invention
Fig. 1 illustrates influence of the relatively thin transition zone to ZnS shell energy band；
Fig. 2 illustrates influence of the thicker transition zone to ZnS shell energy band；
Fig. 3 shows the electronical display mirror photo of the CdZnSeS quantum dot of the preparation of the embodiment of the present application 1；
Fig. 4 shows the electronical display mirror photo of CdZnSeS/ZnS core-shell quanta dots made from the embodiment of the present application 1.
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.
It should be noted that the term " first ", " second " etc. in the description and claims of this application are to be used for
Similar object is distinguished, without being used to describe a particular order or precedence order.It should be understood that the data used in this way are suitable
It can be interchanged in the case of, so as to embodiments herein described herein.In addition, term " includes " and " having " and they
Any deformation, it is intended that cover it is non-exclusive include, for example, containing the process, method of a series of steps or units, being
System, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include be not clearly listed or
For the intrinsic other step or units of these process, methods, product or equipment.The definition of " layer " (English is monolayer)
With meaning well known in the art, pass through the thickness Extrapolation number of plies.
In the biggish ZnS shell of quantum dot core outer cladding energy band, be conducive to the contact completely cut off between exciton and environment, but
It is that the lattice mismatch degree between ZnS shell and core is often larger, causes ZnS shell that can not wrap thickness, existing disposable cladding
The method of ZnS shell can only coat the very thin number of plies (generally less than 3 layers), and with the increase of ZnS shell thickness, in shell
The defect in portion also will increase, and simultaneous fluorescence quantum yield reduces, and fluorescence half-peak breadth broadens, scale topography monodispersity
It is deteriorated.In the prior art, certain methods be coated between core and ZnS shell certain thickness ZnSe, ZnSeS or
CdZnS etc. be used as transition zone, to reduce lattice mismatchs degree, but still remained during subsequent cladding ZnS shell because of
Shell thickness increase brought by internal flaw the problem of increasing, moreover, the transition zone of cladding also can energy level to quantum dot and
Stability has an impact.Based on the problem present on, the present invention provides a kind of preparation method of core-shell quanta dots, solves ZnS
Shell can not wrap thick problem, can also reduce the defect inside ZnS shell.
Core-shell quanta dots preparation method of the invention the following steps are included:
S1 provides quantum dot core, and the solution comprising quantum dot core is mixed in the reaction vessel with zinc precursor；
Sulphur precursor and transition zone precursor, sulphur precursor and transition is repeatedly added after the completion of step S1 in S2 into reaction vessel
Layer precursor is not added simultaneously, and sulphur precursor and zinc precursors reaction generate multiple ZnS layers, and transition zone precursor is at least raw with zinc precursors reaction
At multiple transition zones, wherein the band gap width of transition zone is less than ZnS layers of band gap width, and the single of control transition zone precursor is added
Amount is so that the thickness of transition zone is no more than 1 layer；
Sulphur precursor is added into reaction vessel after the completion of step S2 by S3, and zinc precursor and sulphur precursors reaction generate ZnS layers,
The system containing core-shell quanta dots is obtained after reaction；
Wherein, the type and dosage for the sulphur precursor being added every time are identical or different, the transition zone precursor being added every time
Type and dosage are identical or different.
Since the band gap width of transition zone is smaller, and the thickness of transition zone is no more than 1 layer, therefore transition zone is to ZnS layers each
Between energy band continuity and the influence of structural continuity can ignore substantially, the present invention is equivalent in quantum dot core outer cladding
The continuous ZnS shell in upper erengy band, and the transition zone that compartment of terrain is present in ZnS shell is mainly used for elimination and is increased by shell thickness
And the internal flaw generated, the stability of core-shell quanta dots is also improved while being conducive to increase the thickness of ZnS shell.
Thickness using the ZnS shell of the core-shell quanta dots of method provided by the invention preparation reaches 9 layers or more, nucleocapsid amount
The fluorescence efficiency of son point is greater than 80%.
In some embodiments, the quantum dot core of step S1 is the quantum dot core of uncoated shell, and quantum dot core can select
From following one kind: CdZnSeS, CdZnSe, CdZnS, CdSe, CdS, CdSeS, InP.
In some embodiments, transition zone precursor includes at least one of quantum dot core anion and/or cation
Precursor, therefore transition zone and quantum dot core have at least one identical element.In other words, transition zone precursor can the amount of only including
The precursor or a kind of precursor of anion of one of son point core cation, also may include a variety of cations in quantum dot core
Precursor or a variety of anion precursor, can also simultaneously include the precursor of several cation in quantum dot core and several
The precursor of anion.
Preferably, transition zone precursor includes one of cadmium precursor, zinc precursor, selenium precursor, sulphur precursor, phosphorus precursor or more
Kind.According to a specific embodiment, transition zone precursor is selenium precursor.According to another specific embodiment, transition zone precursor
For cadmium precursor.According to another specific embodiment, transition zone precursor includes cadmium precursor and sulphur precursor.It is specific according to another
Embodiment, transition zone precursor include cadmium precursor and selenium sulphur mixing precursor (can be understood as simultaneously including sulphur precursor and selenium precursor).
In some embodiments, in step S2, the amount of the substance for the sulphur precursor being added when generating a ZnS layers is denoted as M1, raw
The amount of the substance for the transition precursor being added when at the transition zone adjacent with the ZnS layers is denoted as M2, M1:M2=(5~100): 1.It is above-mentioned
" transition zone " in " generating and the ZnS layers of adjacent transition zone " not only includes the transition zone on the outside of the ZnS, also includes place
Transition zone on the inside of the ZnS.In some cases, a ZnS layers of generation, which can be, is repeatedly added sulphur precursors reaction and is formed
, the amount of the substance for the sulphur precursor being added when generating the ZnS layers is the total amount for the sulphur precursor being repeatedly added.By controlling transition zone
The additional amount of precursor, so that the thickness of transition zone is no more than 1 layer, transition zone can effectively eliminate the defect inside ZnS shell, and
The band structure of ZnS shell is had substantially no effect on, therefore core-shell quanta dots fluorescence quantum yield obtained is high, water resistant oxygen performance is good,
Stability is high.
The entire synthesis process of core-shell quanta dots of the invention is simple, and influence factor is few, reproducible, is applicable to various
The quantum dot epitaxial growth ZnS shell of type.
Zinc precursor described in the present invention can be but not limited to zinc polycarboxylate, and cadmium precursor can be but not limited to carboxylic acid cadmium, sulphur
Precursor can be but not limited to S-ODE solution, trialkyl phosphine sulphur, mercaptan, selenium precursor can be but not limited to Se-ODE suspension,
Se-ODE solution, trialkyl phosphine selenium.
The present invention also provides a kind of core-shell quanta dots, including quantum dot core and it is coated on the outermost ZnS of quantum dot core
Shell, the thickness of ZnS shell are greater than 9 layers, and there are multiple transition zones namely multiple transition zones to incite somebody to action radially spacedly for ZnS shell
ZnS shell is divided into ZnS layers multiple, and each ZnS layers of thickness can be the same or different, and the band gap width of each transition zone is less than
The thickness of ZnS layers of band gap width, transition zone is no more than 1 layer, so that two ZnS layers of band structure connects substantially before and after transition zone
ZnS shell outside continuous namely quantum dot core is the substantially continuous shell of band structure.
The outermost that ZnS shell is coated on quantum dot core refers to: core-shell quanta dots no longer coat other shells outside ZnS shell
Layer.
ZnS shell thickness is greater than 9 layers, refers to that ZnS shell has 9 layers or more of ZnS monolayer.The thickness of monolayer
It can also can generally be calculated according to cell parameter, one layer of thickness is about 0.3~0.35nm according to the calculation of bond length of chemical bond.
ZnS Shell Materials have bigger energy band compared with CdS Shell Materials, can be in the optics and chemistry of quantum dot
It is brought in stability preferably as a result, being also beneficial to reduce the cost of shell.The ZnS shell of core-shell quanta dots provided by the invention
Thickness reach 9 layers or more, ZnS shell can completely cut off the contact between exciton and environment well.
Further, the thickness of ZnS shell is less than or equal to 30 layers.The thickness of shell should not be too thick, and too thick shell can limit
Application of the core-shell quanta dots processed in fields such as biomarker, imagings.
Further, the fluorescence efficiency of the core-shell quanta dots is greater than 80%.
It is noted that transition zone may be coated on completely on previous ZnS layer, therefore aforementioned " transition zone is by ZnS
Shell is divided into ZnS layers multiple " it is not proper complete separation, also include the case where that part separates.Control can be passed through
System forms the additive amount of the reactant of transition zone to control the thickness of transition zone, guarantees that the thickness of transition zone is no more than one layer.
In some embodiments, transition zone includes at least one of quantum dot core anion and/or cation, transition zone
It further include Zn element and/or S element.In other words, transition zone and quantum dot core have at least one identical element, transition zone with
ZnS layers have at least one identical element.Transition zone is used to eliminate the internal flaw for being increased by shell thickness and being generated, and is conducive to
The stability of core-shell quanta dots can be improved in the thickness for increasing ZnS shell simultaneously.The material of each transition zone can be identical or not
Together.
Fig. 1 is the schematic diagram of the transition zone in ZnS shell there are multiple thickness no more than 1 layer, when the thickness foot of transition zone
Small on the influence of the energy band of ZnS shell when enough thin, each ZnS layers of energy band is substantially continuous, and transition zone is to nucleocapsid quantum at this time
The level structure of point does not influence substantially.
It there are the thickness of the schematic diagram of multiple thick transition zones namely transition zone is more than 1 layer that Fig. 2, which is in ZnS shell,.Work as transition
It when layer is thicker, is affected to the energy band of ZnS shell, it is no longer continuous to may cause each ZnS layers of energy band, transition zone meeting at this time
The level structure of core-shell quanta dots is had an impact.
Fig. 3 is the electronical display mirror photo of CdZnSeS quantum dot prepared by the embodiment of the present application 1, above-mentioned CdZnSeS quantum
The average grain diameter of point is 7.5nm.
Fig. 4 is that the CdZnSeS quantum dot in Fig. 3 coats the CdZnSeS/ that ZnS shell obtains using the method for embodiment 1
The electronical display mirror photo of ZnS core shell quantum dot, the average grain diameter of above-mentioned CdZnSeS/ZnS core-shell quanta dots are 16nm, this Shen
The thickness of ZnS shell please is significantly higher than the prior art.
In some embodiments, quantum dot core is in CdSe, CdZnSeS, CdZnSe, CdZnS, CdSe, CdS, CdSeS
One kind；Each transition zone is independently selected from one or more of: ZnSe, ZnSeS, CdZnS, CdZnSeS, CdZnSe.
In some embodiments, quantum dot core is InP, and each transition zone is independently selected from one or more of: InZnS,
InZnSe、InZnSeS、ZnPSe、ZnPS。
The present invention also provides a kind of quantum dot optoelectronic devices, including the nucleocapsid quantum as made from aforementioned preparation process of the present invention
Point, or including present invention core-shell quanta dots above-mentioned.Quantum dot optoelectronic devices can be but not limited to photic/electroluminescent display
Part, photic/electroluminescent illuminating device, sensor etc..
The preparation of Se-S-TOP solution (Se:S=3:2): 0.64g S, 1.58g Se is taken to be placed in the vial of 20mL rubber plug
Middle sealing injects 10mL TOP with inert gas discharge wherein air, by this mixture repeatedly oscillating ultrasonic until Se, S are abundant
Dissolution.The Se-S-TOP solution for configuring other concentration need to only change the amount of Se, S.
The preparation of 2mmol/mL S-TOP solution: it takes 0.64g S to be placed in the vial of 20mL rubber plug and seals, use indifferent gas
Body discharge wherein air, injects 10mL TOP, by this mixture repeatedly oscillating ultrasonic until S sufficiently dissolves.
The preparation (Se-SUS) of 1mmol/mL selenium powder suspension: selenium powder (0.8g, 10mmol, 100 mesh or 200 mesh) are dispersed
Into the ODE of 10mL, ultrasound is configured to the suspension of 0.5mmol/mL for 5 minutes.The preparation of the selenium powder suspension of other concentration with
This is similar, need to only change the amount of selenium powder；Using preceding with hand even.
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.
The preparation of 0.5mmol/mL S-TOP solution: taking 2.5mL concentration is the S-TOP solution of 2mmol/mL, and 7.5mL is added
ODE is uniformly mixed.
Method of purification: it takes 10mL stoste in 50mL centrifuge tube, 40mL acetone is added, 50 DEG C are heated to about, then with 8000
Rev/min speed high speed centrifugation precipitate 3 minutes, take out, outwell supernatant, sediment be dissolved in a certain amount of toluene.
[embodiment 1]
The synthesis of CdZnSeS alloy quantum dot: take 4mmol zinc acetate, 0.4mmol cadmium acetate, 20g ODE in tri- neck of 100mL
In flask, at 200 DEG C, it is passed through inert gas and is vented 30 minutes, increase temperature to 300 DEG C, inject 1mL Se-S-TOP solution
(Se:S=3:2), the reaction was continued 20 minutes, stops reaction, purifies CdZnSeS alloy quantum dot obtained and is dissolved in a small amount of ODE.
The synthesis of CdZnSeS/ZnS core-shell quanta dots:
(1) it takes 4mmol zinc acetate, 4.2g oleic acid, 10mL ODE in 100mL three-neck flask, at 200 DEG C, is passed through inertia
Gas exhaust 30 minutes, temperature was increased to 300 DEG C, injects the CdZnSeS alloy quantum dot purified；
(2) 2mL concentration is added dropwise as 0.5mmol/mL S-TOP solution with the speed of 6mL/h, being then injected into 0.1mL concentration is
The Se-TBP solution of 2mmol/mL reacts 5 minutes；
(3) after repetitive operation step (2) five times, 4mL concentration is added dropwise as the S- of 0.5mmol/mL with the speed of 6mL/h again
TOP solution stops reaction.
[embodiment 2]
Embodiment 2 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: 2mL concentration is added dropwise as 0.5mmol/mL S-TOP solution with the speed of 6mL/h, is then injected into the Se-S- of 0.1mL
TOP solution (Se:S=1.3:2) reacts 5 minutes.
[embodiment 3]
Embodiment 3 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: 2mL concentration is added dropwise as 0.5mmol/mL S-TOP solution with the speed of 6mL/h, is then injected into the Se-S- of 0.1mL
TOP solution (Se:S=2.5:1.5) reacts 5 minutes.
[embodiment 4]
Embodiment 4 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) and step (3) are substituted by following steps: it is molten for the S-TOP of 0.5mmol/mL that 10mL concentration is added dropwise with the speed of 6mL/h
Liquid, every S-TOP solution that 2mL is added dropwise then injects the oleic acid cadmium solution that 0.1mL concentration is 0.2mmol/mL, finally with 6mL/h's
The S-TOP solution that 4mL concentration is 0.5mmol/mL is added dropwise in speed, stops reaction.
[embodiment 5]
Embodiment 5 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: it is the S-TOP solution of 0.5mmol/mL that 2mL concentration, which is added dropwise, with the speed of 6mL/h, is then added dropwise at a same speed
The mixed solution for the cadmium oleate that the S-TOP and 0.1mL concentration that 0.1mL concentration is 2mmol/mL is 0.2mmol/mL.
[embodiment 6]
Embodiment 6 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: it is the S-TOP solution of 0.5mmol/mL that 2mL concentration, which is added dropwise, with the speed of 6mL/h, is then added dropwise at a same speed
The Se-S-TOP solution (Se:S=1.3:2) and 0.1mL concentration of 0.1mL is the mixed solution of the cadmium oleate of 0.2mmol/mL.
[embodiment 7]
Embodiment 7 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: it is the S-TOP solution of 0.5mmol/mL that 2mL concentration, which is added dropwise, with the speed of 6mL/h, is then added dropwise at a same speed
The mixed solution for the cadmium oleate that the Se-TBP and 0.1mL concentration that 0.1mL concentration is 2mmol/mL is 0.2mmol/mL.
[embodiment 8]
The synthesis of CdSe quantum dot (the first exciton absorption peak is 550nm, absorbance 50, partial size 3.3nm, spherical shape): will
CdO (0.0256g, 0.2mmol), stearic acid HSt (0.1420g, 0.5mmol) and ODE (4mL) are put into 25mL three-necked bottle, are stirred
It mixes ventilation (argon gas) after ten minutes, is warming up to 280 DEG C, obtains clear solution, be cooled to 250 DEG C, be 0.1mmol/ by 1mL concentration
The selenium powder suspension of mL is rapidly injected in three-necked bottle, and reaction temperature is controlled at 250 DEG C, after reaction 7 minutes, every 2-3 points
Clock, be rapidly injected 0.05mL concentration be 0.1mmol/mL selenium powder suspension, until the size of quantum dot reach target size (
In reaction process, a certain amount of reaction solution is taken to be injected into the quartz colorimetric utensil containing 1-2mL toluene, carries out UV, visible light suction
Receive the measurement of spectrum and fluorescence spectrum), stop heating immediately, purifies CdSe quantum dot obtained and be dissolved in a small amount of ODE.
The synthesis of CdSe/ZnS core-shell quanta dots:
(1) it takes 4mmol zinc acetate, 4.2g oleic acid, 10mLODE in 100mL three-neck flask, at 200 DEG C, is passed through indifferent gas
Body is vented 30 minutes, is increased temperature to 300 DEG C, is injected CdSe quantum dot solution；
(2) 2mL concentration is added dropwise with the speed of 6mL/h is the S-TOP solution of 0.5mmol/mL, is then injected into 0.1mL concentration
For the Se-TBP solution of 2mmol/mL, react 5 minutes；
(3) repetitive operation step (2) three times after, the S- that 4mL concentration is 0.5mmol/mL is added dropwise with the speed of 6mL/h again
TOP solution stops reaction.
[embodiment 9]
The synthesis of CdZnSe quantum dot: weigh basic zinc carbonate (0.66g, 1.2mmol), oleic acid (4.2g, 15mmol),
10g ODE is vented 10 minutes in 100mL three-neck flask with inert gas, is increased temperature to 280 DEG C, is obtained clear solution, drops
Temperature injects 1mL TOP to 200 DEG C, and temperature control is at 200 DEG C, the Se-ODE suspension that injection 0.5mL concentration is 1mmol/mL, reaction
10 minutes, then, injection 1.5mL concentration be 0.2mmol/mL oleic acid cadmium solution, directly increase reaction temperature to 310 DEG C, after
Continuous reaction 20min (during the reaction, take a certain amount of reaction solution to be injected into the quartz colorimetric utensil containing 1-2mL toluene,
Carry out the measurement of ultraviolet-visible absorption spectroscopy and fluorescence spectrum), it purifies CdZnSe quantum dot obtained and is dissolved in a small amount of ODE.
The synthesis of CdZnSe/ZnS core-shell quanta dots:
(1) it takes 4mmol zinc acetate, 4.2g oleic acid, 10mL ODE in 100mL three-neck flask, at 200 DEG C, is passed through inertia
Gas exhaust 30 minutes, temperature was increased to 300 DEG C, injects CdZnSe quantum dot solution；
(2) 2mL concentration is added dropwise with the speed of 6mL/h is the S-TOP solution of 0.5mmol/mL, is then injected into 0.1mL concentration
For the Se-TBP solution of 2mmol/mL, react 5 minutes；
(3) after repetitive operation step (2) five times, 4mL concentration is added dropwise as the S- of 0.5mmol/mL with the speed of 6mL/h again
TOP solution stops reaction.
[embodiment 10]
The synthesis of InP/ZnS core-shell quanta dots:
(1) 0.15mmol (0.043g) indium acetate, 0.45mmol (0.1036g) tetradecylic acid, 10mL ODE is weighed to be put into
It in 50mL three-neck flask, is warming up to 180 DEG C and is vented 30 minutes, reduce temperature to room temperature, inject 0.1mmol (TMS)3P and 1mL
The mixed solution of TOP increases temperature to 260 DEG C, reacts 5 minutes, then reduces temperature to 180 DEG C, injection trioctylphosphine oxide (TOPO) is molten
Liquid reinjects zinc stearate-octadecene solution that 5mL concentration is 1mmol/mL, increases temperature to 260 DEG C；
(2) 1mL concentration is added dropwise with the speed of 6mL/h is the S-TOP solution of 0.5mmol/mL, is then injected into 0.1mL concentration
For the Se-TBP solution of 1mmol/mL, react 5 minutes；
(3) repetitive operation step (2) twice after, the S- that 4mL concentration is 0.5mmol/mL is added dropwise with the speed of 6mL/h again
TOP solution stops reaction.
[comparative example 1]
Comparative example 1 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) are as follows: 2mL concentration is added dropwise as 0.5mmol/mL S-TOP solution with the speed of 6mL/h, being then injected into 0.5mL concentration is
The Se-TBP solution of 2mmol/mL reacts 5 minutes.
[comparative example 2]
Comparative example 1 walks difference from example 1 is that during the synthesis of CdZnSeS/ZnS core-shell quanta dots
Suddenly (2) and step (3) are substituted by following steps: it is molten for the S-TOP of 0.5mmol/mL that 14mL concentration is added dropwise with the speed of 6mL/h
Liquid stops reaction after completion of dropwise addition.
Table 1 lists the fluorescence peak position of each embodiment and comparative example, half-peak breadth, fluorescence efficiency.Wherein quantum dot is sent out
The detection method of light efficiency are as follows: using 450nm blue LED lamp as backlight spectra, test Blue backlight respectively using integrating sphere
Spectrum and the spectrum for penetrating quantum dot composite material utilize the integral area of spectrogram to calculate quantum dot luminous efficiency.Quantum dot hair
Light efficiency=(quantum dot absorption peak area)/(Blue backlight peak area-is through the unabsorbed blue peak face of quantum dot compound
Product) * 100%.
Table 1
Comparing embodiment 1 and the experimental result of comparative example 1 are can be found that: when coating shell, if transition zone precursor is added
Amount it is excessive, will lead to that transition zone is too thick, the fluorescence efficiency of the core-shell quanta dots prepared by is lower.Comparing embodiment 1 with it is right
The experimental result of ratio 2 is can be found that: when coating shell, if not adding transition zone precursor (namely without transition zone in shell),
The fluorescence half-peak breadth of core-shell quanta dots obtained is larger, and fluorescence efficiency is lower.It can be seen that in the shell of core-shell quanta dots
Increasing thickness, suitable transition zone help to obtain the high core-shell quanta dots of narrow half-peak breadth, fluorescence efficiency.
In order to further detect the stability of core-shell quanta dots of the present invention, respectively made from each embodiment and comparative example
Core-shell quanta dots prepare quantum dot film, carry out ageing stability detection (aging condition, 65 DEG C/95% humidity) to quantum dot film,
Quantum dot light emitting efficiency before and after aging is recorded in table 2.
Table 2
Comparing embodiment 1 and the experimental result of comparative example 1 are can be found that: when coating shell, if transition zone precursor is added
Amount it is excessive, will lead to that transition zone is too thick, the stability of the core-shell quanta dots prepared by is poor.Comparing embodiment 1 and comparison
The experimental result of example 2 is can be found that: when coating shell, if not adding transition zone precursor (namely without transition zone in shell), and system
The stability of the core-shell quanta dots obtained is poor.It can be seen that increasing the suitable transition of thickness in the shell of core-shell quanta dots
Layer help to obtain the good core-shell quanta dots of stability.
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 (10)
1. a kind of preparation method of core-shell quanta dots, which comprises the following steps:
S1 provides quantum dot core, and the solution comprising the quantum dot core is mixed in the reaction vessel with zinc precursor；
After the completion of S2, the step S1, sulphur precursor and transition zone precursor, the sulphur precursor is added to the reaction vessel several times
It is not added simultaneously with the transition zone precursor, the sulphur precursor and the zinc precursors reaction generate multiple ZnS layers, the transition zone
Precursor at least generates multiple transition zones with the zinc precursors reaction, wherein the band gap width of the transition zone is less than described ZnS layers
Band gap width, control the transition zone precursor single additional amount make the transition zone thickness be no more than 1 layer；
After the completion of S3, the step S2, sulphur precursor, the zinc precursor and the sulphur precursors reaction are added in Xiang Suoshu reaction vessel
ZnS layers are generated, the system containing core-shell quanta dots is obtained after reaction；
In each step, the sulphur precursor each type and additional amount is identical or different, each kind of the transition zone precursor
Class and additional amount are identical or different.
2. the preparation method of core-shell quanta dots according to claim 1, which is characterized in that the quantum of the step S1
Point core is selected from following one kind: CdZnSeS, CdZnSe, CdZnS, CdSe, CdS, CdSeS, InP.
3. the preparation method of core-shell quanta dots according to claim 1, which is characterized in that the transition zone precursor includes institute
State the precursor of at least one of quantum dot core anion and/or cation, it is preferable that the transition zone precursor includes with next
Kind is a variety of: cadmium precursor, zinc precursor, selenium precursor, sulphur precursor, phosphorus precursor.
4. the preparation method of core-shell quanta dots according to claim 1 to 3, which is characterized in that in the step S2,
Generate one it is ZnS layers described when the amount of the substance of the sulphur precursor that is added be denoted as M1, generate with ZnS described in this layers it is adjacent described
The amount of the substance for the transition precursor being added when transition zone is denoted as M2, M1:M2=(5~100): 1.
5. a kind of core-shell quanta dots, which is characterized in that including quantum dot core and be coated on the outermost ZnS of quantum dot core
Shell, the thickness of the ZnS shell are greater than 9 layers, and there are multiple transition zones radially spacedly for the ZnS shell, multiple described
The ZnS shell is divided into ZnS layers multiple by transition zone, and the band gap width of each transition zone is less than ZnS layers of the band gap
The thickness of width, the transition zone is no more than 1 layer.
6. core-shell quanta dots according to claim 5, which is characterized in that the thickness of the ZnS shell is less than or equal to 30 layers.
7. core-shell quanta dots according to claim 5, which is characterized in that the quantum dot core be selected from CdSe, CdZnSeS,
One of CdZnSe, CdZnS, CdSe, CdS, CdSeS, InP.
8. according to any core-shell quanta dots of claim 5-7, which is characterized in that the fluorescence efficiency of the core-shell quanta dots
Greater than 80%.
9. according to any core-shell quanta dots of claim 5-7, which is characterized in that each transition zone is identical or not phase
Together, the transition zone and the quantum dot core have at least one identical element, and the transition zone has at least one with described ZnS layers
The identical element of kind.
10. a kind of quantum dot optoelectronic devices, which is characterized in that the quantum dot optoelectronic devices include: any by claim 1-4
Any nucleocapsid quantum of the quantum dot or claim 5-9 that the preparation method of the core-shell quanta dots is prepared
Point.
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| CN111509142A (en) * | 2020-03-18 | 2020-08-07 | 纳晶科技股份有限公司 | Core-shell quantum dot, quantum dot light-emitting diode, quantum dot composition and display device |
| CN112824481A (en) * | 2019-11-21 | 2021-05-21 | 纳晶科技股份有限公司 | Quantum dot and preparation method and application thereof |
| CN112961668A (en) * | 2019-12-12 | 2021-06-15 | 浙江纳晶科技有限公司 | Alloy quantum dot, preparation method and application thereof |
| CN113795566A (en) * | 2020-03-30 | 2021-12-14 | 京东方科技集团股份有限公司 | Quantum dot structure, manufacturing method thereof and quantum dot light-emitting device |
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| CN103074068A (en) * | 2013-01-18 | 2013-05-01 | 吉林大学 | Thermosensitive quantum dot material with core-shell structure and preparation method thereof |
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| CN112824481A (en) * | 2019-11-21 | 2021-05-21 | 纳晶科技股份有限公司 | Quantum dot and preparation method and application thereof |
| WO2021098857A1 (en) * | 2019-11-21 | 2021-05-27 | 纳晶科技股份有限公司 | Quantum dot and method for preparing same, and quantum dot composition and photoelectric device |
| CN112961668A (en) * | 2019-12-12 | 2021-06-15 | 浙江纳晶科技有限公司 | Alloy quantum dot, preparation method and application thereof |
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| CN111509142A (en) * | 2020-03-18 | 2020-08-07 | 纳晶科技股份有限公司 | Core-shell quantum dot, quantum dot light-emitting diode, quantum dot composition and display device |
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