CN110373177A - Quantum dot and preparation method thereof - Google Patents
Quantum dot and preparation method thereof Download PDFInfo
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- CN110373177A CN110373177A CN201910535771.3A CN201910535771A CN110373177A CN 110373177 A CN110373177 A CN 110373177A CN 201910535771 A CN201910535771 A CN 201910535771A CN 110373177 A CN110373177 A CN 110373177A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
Abstract
The present invention relates to a kind of quantum dots and preparation method thereof.Above-mentioned quantum dot includes stratum nucleare and shell, the component of the material of stratum nucleare includes P elements, phosphide element, Zn-ef ficiency and element sulphur, the radius of stratum nucleare is 2nm~6nm, shell with a thickness of 8nm~16nm, shell includes the hypostracum being coated on stratum nucleare and the outer shell that is coated on hypostracum, the material of hypostracum is selected from one of ZnSeS and ZnSe, and the material of outer shell is ZnS.The half-peak breadth of above-mentioned quantum dot is up to 78% in 40nm or so, quantum yield.
Description
Technical field
The present invention relates to quantum dot preparation fields, more particularly to a kind of quantum dot and preparation method thereof.
Background technique
Quantum dot is also known as semiconductor nano, is in almost spherical, and three-dimensional radius has bright within the scope of 2nm~20nm
Aobvious quantum effect.Quantum dot is generally by II-VI group element (such as CdS, CdSe, CdTe, ZnSe, ZnS) or iii-v element
Semiconductor materials such as (such as InP, InAs) are constituted, and can also constitute core/shell structure by two or more semiconductor material
Quantum dot (such as common CdSe/ZnS core/shell structure quantum dot).Quantum dot has wide absorption spectrum, narrow and symmetrically send out
The advantages that spectrum, good light stability, quantum yield are high, launch wavelength is adjustable is penetrated, display, medicine, biology, the sun are widely used in
Energy battery, the big field of the energy five, wherein the development of display field is most to enter human lives fastly.
CdSe quantum dot develops fairly perfect at present, has the advantages that half-peak breadth is small, luminous efficiency is high, and still, Cd is weight
Metal, to environment and human body nocuousness, the country such as European Union forbids the use of heavy metal Cd, therefore CdSe quantum dot is unfavorable for business
Development.
III-V compound quantum dot is free of heavy metal element using indium phosphide quantum dot as representative, and no intrinsic toxicity is green
Colour circle is protected, and industrialized production and application are more applicable for, in addition, such quantum dot is formed by covalent bonding, compared to by from
Traditional II-VI group compound quantum dot made of sub-key bonding, has more perfect structure, becomes researcher concern
Focus.
But since the development of InP quantum dot is also immature, there is a problem of that half-peak breadth is wider, luminous efficiency is lower.
Summary of the invention
Based on this, it is necessary to provide that a kind of half-peak breadth is relatively narrow and the higher quantum dot of luminous efficiency.
In addition, also providing a kind of preparation method of quantum dot.
A kind of quantum dot, including stratum nucleare and shell, the component of the material of the stratum nucleare include P elements, phosphide element,
Zn-ef ficiency and element sulphur, the radius of the stratum nucleare are 2nm~6nm, the shell with a thickness of 8nm~16nm, the shell packet
The material of the outer shell for including the hypostracum being coated on the stratum nucleare and being coated on the hypostracum, the hypostracum is selected from
One of ZnSeS and ZnSe, the material of the outer shell are ZnS.
In one of the embodiments, in the stratum nucleare, the molar ratio of the Zn-ef ficiency and the phosphide element is 1.1: 5.0
~5.0: 1.1；And/or
The molar ratio of the P elements and the phosphide element is 0.1: 1.0~3.0: 1.0；And/or
The molar ratio of the element sulphur and the phosphide element is 0.1: 1.0~2.0: 1.0.
The ratio of the radius of the thickness of the shell and the stratum nucleare is 1: 1~6: 1 in one of the embodiments,.
The number of plies of the hypostracum is 10 layers~20 layers in one of the embodiments, and the number of plies of the outer shell is 1 layer
~10 layers.
A kind of preparation method of quantum dot, includes the following steps:
First zinc source and indium source are added in the first mixed liquor, then are warming up to 100 DEG C~200 DEG C reactions, obtains first
Reaction solution contains ligand and non-complexing solvent in first mixed liquor；
Phosphorus source and the first sulphur source are added in first reaction solution, then are warming up to 200 DEG C~300 DEG C reactions, is obtained
Second reaction solution；
At least one of selenium source and the second sulphur source are mixed with second reaction solution and the second mixed liquor, then are warming up to
250 DEG C~300 DEG C reactions obtain third reaction solution, contain the second zinc source in second mixed liquor；And
Third zinc source and third sulphur source are added in the third reaction solution, then are warming up to 300 DEG C~350 DEG C reactions,
Obtain quantum dot.
The step that the first zinc source is added in the first mixed liquor with indium source includes: in one of the embodiments,
Wiring solution-forming is distinguished into first zinc source and the indium source, then institute is injected into simultaneously with the rate of 10mL/min~20mL/min
It states in the first mixed liquor；And/or
The step that phosphorus source and the first sulphur source are added in first reaction solution includes: by phosphorus source and described
First sulphur source wiring solution-forming, then be injected into first reaction solution with the rate of 20mL/min~40mL/min.
In one of the embodiments, it is described by least one of selenium source and the second sulphur source and second reaction solution and
The step of second mixed liquor mixes includes: that second reaction solution is first injected into institute with the rate of 10mL/min~20mL/min
State in the second mixed liquor, then with the rate of 0.1mL/min~2.0mL/min by the selenium source and second sulphur source at least
One kind is injected into second mixed liquor.
It is described in one of the embodiments, that third zinc source and third sulphur source are added to the step in the third reaction solution
It suddenly include: to be infused by third zinc source and the third sulphur source wiring solution-forming, then with the rate of 0.1mL/min~2.0mL/min
It is mapped in the third reaction solution.
It is described in one of the embodiments, that the first zinc source and indium source are added in the first mixed liquor, then it is warming up to 100
DEG C~200 DEG C of reactions the step of in, temperature be 130 DEG C~150 DEG C, the reaction time be 1min~60min.
It is described in one of the embodiments, that phosphorus source and the first sulphur source are added in first reaction solution, then heat up
Into the step of 200 DEG C~300 DEG C reactions, temperature is 250 DEG C~280 DEG C, and the reaction time is 10min~100min.
Above-mentioned quantum dot, which passes through, selects phosphorus, indium, sulphur and Zn-ef ficiency as the component of core layer material, and in stratum nucleare outsourcing
Wrap up in specific hypostracum and outer shell, and adjust the radius of stratum nucleare and the thickness of shell, the half-peak breadth of the quantum dot made compared with
Narrow, luminous efficiency is higher.It is demonstrated experimentally that the half-peak breadth of above-mentioned quantum dot, in 40nm or so, luminous efficiency is up to 78%.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of the quantum dot of an embodiment；
Fig. 2 is the ultraviolet spectrogram of the ZnInPS quantum dot core in embodiment 1；
Fig. 3 is the fluorescence spectra of the ZnInPS/ZnSeS/ZnS quantum dot in embodiment 1；
Fig. 4 is the TEM figure of the ZnInPS/ZnSeS/ZnS quantum dot in embodiment 1.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiment to invention is more fully described.Tool
Preferred embodiment of the invention is given in body embodiment.But the invention can be realized in many different forms,
It is not limited to the examples described herein.On the contrary, purpose of providing these embodiments is makes to the disclosure
Understanding it is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
Body embodiment purpose, it is not intended that in limitation the present invention.
It should be noted that, in this document, the thickness of shell and partial size, the outer shell radius of quantum dot are same general
It reads, indicates total radius size of stratum nucleare and shell.
The quantum dot of one embodiment, including stratum nucleare and shell, the component of the material of stratum nucleare include P elements, indium member
Element, Zn-ef ficiency and element sulphur, the radius of stratum nucleare are 2nm~6nm, shell with a thickness of 8nm~16nm, shell is coated on core
The material of hypostracum on layer and the outer shell being coated on hypostracum, hypostracum is selected from one of ZnSeS and ZnSe, shell
The material of layer is ZnS.
Specifically, in stratum nucleare, the molar ratio between Zn-ef ficiency and phosphide element is 1.1: 5.0~5.0: 1.1.Further,
Molar ratio between Zn-ef ficiency and phosphide element is 1.1: 3.0~3.0: 1.1.It sets the molar ratio of Zn-ef ficiency and phosphide element to
The effect for stating value is: when the Zn-ef ficiency under the molar ratio is reacted with phosphide element with subsequent P elements and element sulphur, the lattice of formation
Symmetrical configuration and complete, stability is high, furthermore target wavelength and partial size in order to obtain, adjusts the ratio, can achieve adjusting wave
Long and partial size effect.
In stratum nucleare, the molar ratio between P elements and phosphide element is 0.1: 1.0~3.0: 1.0.Further, P elements with
Molar ratio between phosphide element is 0.5: 1.0~2.0: 1.0.Set the molar ratio of P elements and phosphide element in the work of above-mentioned value
With being: the reactivity between P elements and phosphide element under the molar ratio can reach an optimum state, in the reactivity
Under P elements when being reacted with phosphide element, Zn-ef ficiency and element sulphur, can be combined with an iptimum speed, be conducive to the uniform of result
Property, it may have the effect of adjusting wavelength and partial size.
Molar ratio between element sulphur and phosphide element is 0.1: 1.0~2.0: 1.0.Further, element sulphur and phosphide element
Between molar ratio be 0.2: 1.0~0.5: 1.0.It is by the effect that the molar ratio of element sulphur and phosphide element is set as above-mentioned value:
When element sulphur under the molar ratio is reacted with phosphide element with P elements and Zn-ef ficiency, the lattice structure of formation is symmetrical and complete, surely
Qualitative height, furthermore target wavelength and partial size in order to obtain, adjust the ratio, can achieve the effect of adjusting wavelength and partial size.
Zn-ef ficiency and element sulphur are introduced in InP quantum dot core, the radius of quantum dot stratum nucleare can be made bigger, improve InP
The quantum yield of quantum dot stratum nucleare.
Specifically, the number of plies of hypostracum is 10 layers~20 layers.The number of plies of outer shell is 1 layer~10 layers.The effect of hypostracum
It is control wavelength, the effect of outer shell is can preferably to reduce lattice defect, to improve luminous efficiency.
Specifically, the ratio of the radius of the thickness and stratum nucleare of shell is 1: 1~6: 1.By the radius of the thickness of shell and stratum nucleare
Ratio be set as the effect of above-mentioned value and be: regulate and control the wavelength of quantum dot, lattice defect can be effectively reduced, improve
Luminous efficiency.
In stratum nucleare outer cladding ZnS shell, the generation of InP non-radiative recombination can reduce, but ZnS is adapted to the lattice of InP
Spend it is larger, be easy interface generate defect, ZnS is more difficult in cladding is effectively grown in the surface InP, and quantum yield is caused to drop
Low, stability is poor.And the lattice constant gap of ZnSe or ZnSeS and InP is smaller, is easy to be coated on stratum nucleare surface.Therefore, first
In stratum nucleare outer cladding ZnSe or ZnSeS, then ZnS layers are coated, so that the lattice collocation degree of stratum nucleare and shell is smaller, to be conducive to
Improve the quantum yield of quantum dot.
The thickness of shell is thicker in above-mentioned quantum dot, so that the quantum yield of the quantum dot made is higher, half-peak breadth compared with
It is narrow.
Above-mentioned quantum dot has at least the following advantages:
(1) quantum yield of above-mentioned quantum dot is up to 78%, and half-peak breadth is in 40nm or so, and half-peak breadth is narrower, so that grain
The homogeneity of son is better, and the color that quantum dot is issued is purer.
(2) environmentally harmful cadmium element is not contained in above-mentioned quantum dot, is had the advantages that environmentally protective.
Referring to Fig. 1, the preparation method of the quantum dot of an embodiment, includes the following steps:
Step S110: the first ligand and the first non-complexing solvent being mixed, then are warming up to 50 DEG C~150 DEG C, form first
Mixed liquor.
Further, the first ligand and the first non-complexing solvent are mixed, and in the step of being warming up to 50 DEG C~150 DEG C,
Temperature is preferably 70 DEG C~110 DEG C.
Wherein, the first ligand plays the role of coordination stability, and the first non-complexing solvent plays dissolution and dispersion reactant
Effect.
Step S120: the first zinc source and indium source being added in the first mixed liquor, then are warming up to 100 DEG C~200 DEG C reactions,
Form the first reaction solution.
Specifically, the step the first zinc source and indium source being added in the first mixed liquor includes: by the first zinc source and indium source
Wiring solution-forming respectively, then be injected into the first mixed liquor simultaneously with the rate of 10mL/min~20mL/min.
In the step of the first zinc source and indium source difference wiring solution-forming, the second non-complexing solvent and the non-network of third is respectively adopted
Bonding solvent is by the first zinc source and indium source is dissolved and wiring solution-forming.It is appreciated that the second non-complexing solvent and third non-complexing solvent
Be in order to dissolve or disperse the first zinc source and indium source, when the first zinc source or indium source are solution, the second non-complexing solvent or third
Non-complexing solvent also can be omitted.
Using above-mentioned injection rate, obtained lattice structure is most stable, as a result preferably, if being higher than this speed response meeting
Compare acutely, solution can be gone in condenser pipe, and solution loss or pollution are caused, unfavorable to reaction result.
Further, the first zinc source and indium source are added in the first mixed liquor, then are warming up to 100 DEG C~200 DEG C reactions
The step of in, temperature is preferably 130 DEG C~150 DEG C.Reaction time is 1min~60min.
It further, further include being mixed first before the step the first zinc source and indium source being added in the first mixed liquor
The step of closing liquid degasification.The time of degasification is 10min~90min.Further, the time of degasification is 10min~60min.It removes
The purpose of gas is to carry out subsequent reactions under inert gas protection.Inert gas can be nitrogen, argon gas etc..
Step S130: phosphorus source and the first sulphur source are added in the first reaction solution, are warming up to 200 DEG C~300 DEG C reactions, are obtained
To the second reaction solution.
By the step that phosphorus source and the first sulphur source are added in the first reaction solution include: phosphorus source and the first sulphur source are made into it is molten
Liquid, then be injected into the first reaction solution with the rate of 20mL/min~40mL/min.Quantum can be made using above-mentioned injection rate
Point homogeneous nucleation.
In the step of phosphorus source and the first sulphur source wiring solution-forming, phosphorus source and the first sulphur source are matched using the 4th non-complexing solvent
At solution.It is appreciated that the 4th non-complexing solvent can be omitted when phosphorus source and the first sulphur source are solution.
Further, phosphorus source and the first sulphur source are added in the first reaction solution, are warming up to 200 DEG C~300 DEG C reactions
In step, temperature is preferably 250 DEG C~280 DEG C.Reaction time is 10min~100min.
In above-mentioned nucleation process, the temperature of nucleation is lower, is conducive to the stability of lattice structure, and temperature is excessively high, can shape
At precipitated metal, it is unfavorable for being nucleated.During nucleus growth, temperature is higher, is conducive to the growth of nucleus.Therefore, above-mentioned
During preparing quantum dot stratum nucleare structure, by the way of gradually heating up, conducive to being stablized and uniform quantum dot core.
Further, first exciton absorption peak position of the above-mentioned ZnInPS quantum dot core under uv-vis spectra exists
It is adjustable within the scope of 400nm~500nm, by adjusting the ratio between Zn, S, P, In, so that the quantum dot of different-grain diameter is obtained,
So as to adjust the wavelength of the quantum dot core.
Step S140: the second zinc source, Ligands and the 5th non-complexing solvent are mixed, then are warming up to 100 DEG C~150
DEG C, form the second mixed liquor.
Further, in step S140, temperature is preferably 110 DEG C~130 DEG C.
Further, Ligands are different from the first ligand, by the second zinc source, Ligands and the 5th non-complexing solvent
It further include the process of ligand exchange in the step of mixing.It is handled by ligand exchange, the activity in the zinc source after exchanging ligand is
Increase, is conducive to and the combination in indium source, phosphorus source and sulphur source.
Step S150: at least one of selenium source and the second sulphur source are mixed with the second reaction solution and the second mixed liquor, then
250 DEG C~300 DEG C reactions are warming up to, third reaction solution is formed.
Further, at least one of selenium source and the second sulphur source are mixed with the second reaction solution and the second mixed liquor, then
In the step of being warming up to 250 DEG C~300 DEG C reactions, temperature is preferably 270 DEG C~290 DEG C.
Specifically, the step of at least one of selenium source and the second sulphur source being mixed with the second reaction solution and the second mixed liquor
Include: first the second reaction solution is injected into the second mixed liquor with the rate of 10mL/m~20mL/min, then with 0.1mL/min~
At least one of selenium source and the second sulphur source are injected into the second mixed liquor by the rate of 2.0mL/min.Using above-mentioned injection speed
Rate is the quantum dot in order to form uniform particle diameter.
Further, the step at least one of selenium source and the second sulphur source mixed with the second reaction solution and the second mixed liquor
Further include the steps that mixing with third ligand in rapid.Third ligand is injected into the second mixed liquor.
In the present embodiment, the effect that third ligand is added is to improve the activity of the second reaction solution, it will be understood that second
When the activity of reaction solution is higher, third ligand also be can be omitted.
Further, the step at least one of selenium source and the second sulphur source mixed with the second reaction solution and the second mixed liquor
Before rapid, further include the steps that degasification.Specifically, the step of degasification include: at 100 DEG C~150 DEG C carry out degasification 10min~
90min.Further, in the step of degasification, temperature is 100 DEG C~130 DEG C, and the degasification time is 10min~60min.
Step S160: third zinc source and third sulphur source being added in third reaction solution, then are warming up to 300 DEG C~350 DEG C,
Form the 4th reaction solution.
Further, third zinc source and third sulphur source are added in third reaction solution, and are warming up to 300 DEG C~350 DEG C
The step of in, temperature is preferably 310 DEG C~330 DEG C.
Specifically, step third zinc source and third sulphur source being added in third reaction solution include: by third zinc source with
Third sulphur source wiring solution-forming, then be injected into third reaction solution with the rate of 0.1mL/min~2.0mL/min.Using above-mentioned note
Firing rate rate is the quantum dot in order to form uniform particle diameter.
In by third zinc source and the step of third sulphur source wiring solution-forming, using the 6th non-complexing solvent by third zinc source and the
Three sulphur source wiring solution-formings.It is appreciated that the 6th non-complexing solvent is in order to dissolve or disperse third zinc source and third sulphur source, when
When three zinc sources and third sulphur source are solution, the 6th non-complexing solvent be can be omitted.
Step S170: the 4th reaction solution is purified, quantum dot is obtained.
Step S170 is specifically included: the 4th reaction solution is down to room temperature, and use volume ratio for 1: 1~1: 5 methanol and
The mixed solvent of n-butanol precipitates the 4th reaction solution, obtains sediment.Sediment is dissolved in toluene again, the amount of obtaining
Sub- point.
In stratum nucleare outer cladding ZnS shell, the generation of InP non-radiative recombination can reduce, but ZnS is adapted to the lattice of InP
Spend it is larger, be easy interface generate defect, ZnS is more difficult in cladding is effectively grown in the surface InP, and quantum yield is caused to drop
Low, stability is poor.And the lattice constant gap of ZnSe or ZnSeS and InP is smaller, is easy to be coated on stratum nucleare surface.Therefore, first
In one layer of ZnSe or ZnSeS of stratum nucleare outer cladding, then coat ZnS layers.
Specifically, the first zinc source used in the preparation step of above-mentioned quantum dot, the second zinc source and third zinc source difference
Independently selected from caproic acid zinc, zinc octoate, zinc laurate, Zinc tetradecanoate, zinc palmitate, zinc dithiocarbamate, diethyl
Zinc, zinc methide, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, nitric acid
Zinc, zinc oleate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, zinc stearate, ten sour zinc, zinc undecylenate and diethyl
At least one of two thiocarbamate zinc.
It is molten that above-mentioned indium source is selected from tributylphosphine indium, indium octadecene solution, indium oleyl amine solution, oleic acid solution of indium, tetradecylic acid indium
At least one of liquid, carbonic acid indium, indium nitrate, indium acetate, stearic acid indium, indium iodide, indium bromide, trimethyl indium and inidum chloride.
Phosphorus source is selected from three (dimethylamino) phosphines, three (diethylin) phosphines, three (trimethylsilyl) phosphines, tri octyl phosphine and three fourths
At least one of base phosphine.
First sulphur source, the second sulphur source and third sulphur source are separately selected from elemental sulfur, hydrogen sulfide, bis- (trimethylsilyls)
At least one of thioether, six amino thioethers and lauryl mercaptan.
Selenium source is selected from selenizing diisobutyl phosphine, trioctylphosphine selenizing phosphine, three (normal-butyl) selenizing phosphines, three (sec-butyl) selenizings
Phosphine, three (tert-butyl) selenizing phosphines, trimethyl selenizing phosphine, triphenyl selenizing phosphine, thricyclohexyl selenizing phosphine, 1- octane selenol, 1- ten
Dioxane selenol, selenophenol, selenium simple substance, hydrogen selenide, bis- (trimethyl silyl) at least one of selenides and selenourea.
First non-complexing solvent, the second non-complexing solvent, third non-complexing solvent, the 4th non-complexing solvent, the 5th non-network
Bonding solvent and the 6th non-complexing solvent are separately selected from least one of alkene, alkane, ether and aromatic compound.Into
One step, the first non-complexing solvent, the second non-complexing solvent, third non-complexing solvent, the 4th non-complexing solvent, the 5th non-complexing
Solvent and the 6th non-complexing solvent are separately selected from phenylbenzene, octadecylene, 19 alkene, icosa alkene, lignocerane, 22
At least one of alkane, eicosane, octadecane, atoleine and isotriacontane.It is above-mentioned, the first non-complexing solvent, the second non-network
Bonding solvent, third non-complexing solvent, the 4th non-complexing solvent, the selection of the 5th non-complexing solvent and the 6th non-complexing solvent are main
Consideration keeps the dissolubility of raw material more preferable, and the variation of cooperation experimental temperature.
First ligand and Ligands are acid ligand.Specifically, the first ligand and Ligands separately select
From at least one of ten acid, undecenoic acid, lauric acid/dodecanoic acid, tridecanoic acid, tetradecylic acid, hexadecylic acid, stearic acid, oleic acid and stearic acid.
The main reactivity for considering raw material of the selection of above-mentioned first ligand and Ligands.
Third ligand is selected from least one of long-chain fat race amine, arylamine class and thio-alcohol.Further, third is matched
Body be selected from lauryl mercaptan, n-octyl mercaptan, oleyl amine, di-n-propylamine, n-hexylamine, n-octyl amine, trioctylamine, eight amine, lauryl amine, cetylamine and
At least one of octadecylamine.
There is core-shell structure by the quantum dot that the preparation method of above-mentioned quantum dot obtains.Wherein, stratum nucleare include P elements,
The radius of phosphide element, Zn-ef ficiency and element sulphur, stratum nucleare is 2nm~6nm, and shell includes the hypostracum being coated on stratum nucleare and cladding
Outer shell on hypostracum, hypostracum be selected from one of ZnSeS and ZnSe, outer shell ZnS, shell with a thickness of 8nm
~16nm, and the ratio of the radius of the thickness and stratum nucleare of shell is 1: 1~6: 1.It is demonstrated experimentally that passing through the preparation side of above-mentioned quantum dot
The quantum yield for the quantum dot that method obtains is up to 78%, and half-peak breadth is in 40nm or so.
The preparation method of above-mentioned quantum dot has at least the following advantages:
(1) preparation method of above-mentioned quantum dot has the advantages that easy to operate, result is stable, favorable repeatability.
(2) half-peak breadth for the quantum dot that the preparation method of above-mentioned quantum dot enables to is in 40nm or so, luminous efficiency
Up to 78%, and using the preparation method of above-mentioned quantum dot, it still can achieve same result when expanding volume production.
(3) preparation method of above-mentioned quantum dot can also be matched by change reaction temperature, injection rate, element and when be reacted
Time etc. adjusts the wavelength and band structure of quantum dot.
The following are specific embodiment parts:
Embodiment 1
The preparation process of the quantum dot of the present embodiment is as follows:
(1) 35mmol oleic acid and 255.8mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 90 DEG C.And carry out
Degasification 30min, reaction later carry out under protection of argon gas.At this temperature, with the rate of 10mL/min by 8.24mmol
Trimethyl indium solution (being dissolved in 20mL octadecylene) and 20.54mmol diethyl zinc solution (being dispersed in 20mmol octadecylene) are equal
It is even to be injected into the first mixed liquor, and temperature is raised to 100 DEG C of heat preservation 30min, obtain the first reaction solution.By 11.86mmol tri-
(trimethylsilyl) phosphine and bis- (trimethyl silicon substrate) thioethers of 1.84mmol are dispersed in 4mL octadecylene, then with the speed of 30mL/min
Rate is injected into the first reaction solution, and temperature is risen to 280 DEG C, reacts 45min, and it is anti-to obtain second containing ZnInPS quantum dot core
Answer liquid.
(2) it by 22.2mmol zinc acetate, 23.35mmol tetradecylic acid and 30mL isotriacontane Hybrid Heating to 130 DEG C, is formed
Second mixed liquor, and degasification 30min, reaction later carry out under protection of argon gas.250 DEG C are warming up to, first with 10mL/min's
21.3mmol lauryl amine and the second reaction solution of 10mmol are injected into the second mixed liquor by rate, then with the rate of 0.1mL/min
The mixed solution of bis- (trimethyl silicon substrate) thioethers of 21.3mmol selenizing diisobutyl phosphine and 2.2mmol is injected into the second mixed liquor
In, to form the ZnSeS shell being coated on ZnInPS core, obtain third reaction solution.Temperature is risen to 300 DEG C, again simultaneously
With the rate of 0.1mL/min by 42mL zinc oleate and bis- (trimethyl silicon substrate) thioethers of 12.5mmol that are dispersed in 39mL octadecylene
It is injected into third reaction solution, keeps the temperature 10min, to form the ZnS shell being coated on ZnSeS shell, obtain the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 with volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSeS/ZnS quantum dot.Wherein, ZnInPS is the stratum nucleare of quantum dot, and ZnSeS is the hypostracum of quantum dot, ZnS
For the outer shell of quantum dot, "/" expression layer.
Embodiment 2
The preparation process of the quantum dot of the present embodiment is the preparation process of quantum dot when expanding volume production, specific as follows:
(1) 140mol oleic acid and lmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 90 DEG C.And carry out degasification
30min, reaction later carry out under protection of argon gas.At this temperature, with the injection rate of 10mL/min by 33mmol tri-
Methyl solution of indium (being dissolved in 80mL octadecylene) and 82.16mmol diethyl zinc solution (being dispersed in 80ml octadecylene) are uniform
It is injected into the first mixed liquor, temperature is then raised to 100 DEG C of heat preservation 30min, obtains the first reaction solution.By 47.44mmol tri-
(trimethylsilyl) phosphine and bis- (trimethyl silicon substrate) thioethers of 7.36mmol are dispersed in 16mL octadecylene, then with the speed of 30mL/min
Rate is injected into the first reaction solution, and temperature is risen to 280 DEG C, reacts 45min, and it is anti-to obtain second containing ZnInPS quantum dot core
Answer liquid.
(2) by 666mmol zinc acetate, 700mmol tetradecylic acid and 900ml isotriacontane Hybrid Heating to 130 DEG C, the is formed
Two mixed liquors, and degasification 30min, reaction later carry out under protection of argon gas.250 DEG C are warming up to, first with 10mL/min's
640mmol lauryl amine and the second reaction solution of 300mmol are injected into the second mixed liquor by rate, then with the rate of 0.1mL/min
Bis- (trimethyl silicon substrate) the thioether mixed solutions of 640mmol selenizing diisobutyl phosphine and 66mmol are injected into the second mixed liquor,
To form the ZnSeS shell being coated on ZnInPS core, third reaction solution is obtained.Temperature is risen to 300 DEG C, again with 0.1mL/
The rate of min simultaneously infuses 1.26L zinc oleate and bis- (trimethyl silicon substrate) thioethers of the 375mmol being dispersed in 1.17L octadecylene
Enter into third reaction solution, finally keep the temperature 10min, to form the ZnS shell being coated on ZnSeS shell, obtains the 4th reaction
Liquid.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 with volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSeS/ZnS quantum dot.
Embodiment 3
The preparation process of the quantum dot of the present embodiment is as follows:
(1) 35mmol tetradecylic acid and 255.81mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 50 DEG C.It goes forward side by side
Row degasification 60min, reaction later carry out under protection of argon gas.It at this temperature, will with the rate of 20mL/min
8.24mmol trimethyl indium solution (being dissolved in 17mL to connect in hexichol) and 6.54mmol diethyl zinc solution (are dispersed in 17ml and connect two
In benzene) it injects uniformly into the first mixed liquor, and temperature is raised to 150 DEG C of heat preservation 30min, obtain the first reaction solution.It will
Bis- (trimethyl silicon substrate) thioethers of the trioctylphosphine selenizing phosphine and 4.12mmol of 16.48mmol are dispersed in 4mL octadecylene, then with
Temperature is risen to 200 DEG C, reacts 45min, obtain by the rate of 40mL/min fast injection at 150 DEG C into the first reaction solution
The second reaction solution containing ZnInPS quantum dot core.
(2) by 22.2mmol zinc stearate, 23.3mmol tetradecylic acid and 30mL isotriacontane Hybrid Heating to 100 DEG C, shape
At the second mixed liquor, and degasification 60min, reaction later carry out under protection of argon gas.300 DEG C are warming up to, first with 10mL/
The second reaction solution of 10mmol is injected into the second mixed liquor by the rate of min, then with the rate of 2mL/min that 21.3mmol tri- is pungent
Base selenizing phosphine is injected into the second mixed liquor, to form the ZnSe shell being coated on ZnInPS core, obtains third reaction solution.It will
Temperature rises to 350 DEG C, again simultaneously by 42mL zinc oleate and the bis- (trimethyl silicanes of 12.5mmol being dispersed in 39mL octadecylene
Base) thioether is injected into third reaction solution, and 40min is reacted, 10min is finally kept the temperature, to form the ZnS being coated on ZnSe shell
Shell obtains the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 by volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSe/ZnS quantum dot.
Embodiment 4
The preparation process of the quantum dot of the present embodiment is as follows:
(1) 35mmol stearic acid and 255.81mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 150 DEG C.And
Degasification 10min is carried out, reaction later carries out under protection of argon gas.It at this temperature, will with the injection rate of 15mL/min
8.24mmol trimethyl indium solution (being dissolved in 17mL phenylbenzene) and 1.81mmol oleic acid zinc solution inject uniformly mixed to first
It closes in liquid, and temperature is raised to 200 DEG C of heat preservation 45min, obtain the first reaction solution.By (trimethylsilyl) phosphine of 4.12mmol tri- and
Bis- (trimethyl silicon substrate) thioethers of 2.47mmol are dispersed in 4mL octadecylene, then are quickly infused at 200 DEG C with the rate of 30mL/min
It is mapped in the first reaction solution, temperature is risen to 300 DEG C, reacts 30min, obtain the second reaction containing ZnInPS quantum dot core
Liquid.
(2) by 22.2mmol zinc stearate, 23.3mmol tetradecylic acid and 30mL isotriacontane Hybrid Heating to 150 DEG C, shape
At the second mixed liquor, and degasification 60min, reaction later carry out under protection of argon gas.270 DEG C are warming up to, first with 20mL/
The second reaction solution of 10mmol is injected into the second mixed liquor by the rate of min, then with the rate of 1mL/min that 21.3mmol tri- is pungent
Base selenizing phosphine and bis- (trimethyl silicon substrate) the thioether mixed solutions of 2.2mmol are injected into the second mixed liquor, are coated on being formed
ZnSeS shell on ZnInPS core, obtains third reaction solution.Temperature is risen to 340 DEG C, again while by 42mL zinc oleate and being divided
Bis- (trimethyl silicon substrate) thioethers of the 12.5mmol being dispersed in 39mL octadecylene are injected into third reaction solution, react 50min, finally
10min is kept the temperature, to form the ZnS shell being coated on ZnSeS shell, obtains the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 by volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSeS/ZnS quantum dot.
Embodiment 5
The preparation process of the quantum dot of the present embodiment is as follows:
(1) 35mmol oleic acid and 255.81mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 90 DEG C.And carry out
Degasification 60min, reaction later carry out under protection of argon gas.90 DEG C are kept the temperature at, while with the injection of 10mL/min
8.24mmol indiumchloride solution (being dissolved in 17mL octadecylene) and 24.72mmol diethyl zinc solution (are dispersed in by rate
In 17ml octadecylene) it injects uniformly into the first mixed liquor, and temperature is raised to 140 DEG C of heat preservation 30min, obtain the first reaction
Liquid.Bis- (trimethyl silicon substrate) thioethers of (dimethylamino) phosphine of 16.48mmol tri- and 8.24mmol are dispersed in 4mL octadecylene, then
With the rate of 20mL/min, temperature is risen to 270 DEG C, reacts 45min, obtain by fast injection into the first reaction solution at 140 DEG C
To the second reaction solution containing ZnInPS quantum dot core.
(2) by 22.2mmol zinc stearate, 23.35mmol tetradecylic acid and 30mL isotriacontane Hybrid Heating to 120 DEG C, shape
At the second mixed liquor, and degasification 30min, reaction later carry out under protection of argon gas.285 DEG C are warming up to, first with 15mL/
The second reaction solution of 10mmol is injected into the second mixed liquor by the rate of min, then with the rate of 0.1mL/min by 21.3mmol tri-
The mixed solution of octyl selenizing phosphine and bis- (trimethyl silicon substrate) thioethers of 2.2mmol is injected into the second mixed liquor, to form cladding
ZnSeS shell on ZnInPS core, obtains third reaction solution.Temperature is risen to 320 DEG C, again simultaneously by 42mL zinc oleate and
Bis- (trimethyl silicon substrate) thioethers of the 12.5mmol being dispersed in the octadecylene of 39mL are injected into third reaction solution, inject 60min,
10min is kept the temperature, to form the ZnS shell being coated on ZnSeS shell, obtains the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 with volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSeS/ZnS quantum dot.
Comparative example 1
The preparation process of quantum dot in comparative example 1 and the difference of the preparation process of the quantum dot in embodiment 1 are: step
Suddenly (1) are as follows: 35mmol oleic acid and 245.8mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 90 DEG C, and carry out degasification
30min, reaction later carry out under protection of argon gas.Temperature is kept for 90 DEG C, is uniformly infused with the injection rate of 10mL/min
8.24mmol trimethyl indium solution (being dissolved in 20mL octadecylene) is penetrated, temperature is then raised to 100 DEG C of heat preservation 30min, obtains
One reaction solution.17.8mmol tri- (trimethylsilyl) phosphine is dispersed in 4mL octadecylene, then with 30mL/min's at 100 DEG C
Rate fast injection rises to 280 DEG C into the first reaction solution, then by temperature, reacts 45min, obtains containing InP quantum dot core
Second reaction solution.
Step (2) and step (3) respectively in embodiment 1 step (2) and step (3) it is identical, obtain InP/ZnSeS/
ZnS quantum dot.
Comparative example 2
The preparation process of quantum dot in comparative example 2 and the difference of the preparation process of the quantum dot in embodiment 1 are: right
T1 in ratio 2 is 90 DEG C, and T2 is 90 DEG C, and T3 is 230 DEG C, and T4 is 130 DEG C, and T5 is 200 DEG C, and T6 is 250 DEG C.Wherein, T1 is
The temperature of first mixed liquor, T2 are the temperature of the first reaction solution, and T3 is the temperature of the second reaction solution, and T4 is the temperature of the second mixed liquor
Degree, T5 are the temperature of third reaction solution, and T6 is the temperature of the 4th reaction solution.
Comparative example 3
The preparation process of quantum dot in comparative example 3 and the difference of the preparation process of the quantum dot in embodiment 1 are: right
V1 in ratio 3 is 30mL/min, v2 10mL/min, v3 5mL/min, v4 2.5mL/min, v5 2.5mL/min.Its
In, v1 indicates for the first zinc source and indium source to be injected into the injection rate in the first mixed liquor, and v2 is indicated phosphorus source and the first sulphur source
Third ligand and the second reaction solution are injected into the second mixed liquor by the injection rate being injected into the first reaction solution, v3 expression
Selenium source and the second sulphur source are injected into the injection rate in the second mixed liquor by injection rate, v4 expression, and v5 is indicated third zinc source
The injection rate in third reaction solution is injected into third sulphur source.
Comparative example 4
The preparation process of quantum dot in comparative example 4 is as follows:
(1) 35mmol oleic acid, 255.8mmol octadecylene Hybrid Heating are obtained into the first mixed liquor to 300 DEG C.And by
One mixed liquor carries out degasification 30min, and reaction later carries out under protection of argon gas.Simultaneously by 8.24mmol trimethyl indium solution
(being dissolved in 17mL octadecylene) and 10.54mmol diethyl zinc solution (being dispersed in 17ml octadecylene) are added to the first mixing
In liquid, the first reaction solution is obtained.By bis- (trimethyl silicon substrate) the thioether dispersions of (trimethylsilyl) phosphine of 7.8mmol tri- and 1.84mmol
Fast injection reacts 60min into the first reaction solution in 4mL octadecylene, and it is anti-to obtain second containing ZnInPS quantum dot core
Answer liquid.
(2) reaction temperature is down to 150 DEG C, 22.2mmol zinc acetate is added, be vented 30min, be warming up to 260 DEG C, be added
21.3mmol selenizing diisobutyl phosphine reacts 20min, to form the ZnSe shell being coated on ZnInPS core, adds dispersion
Bis- (trimethyl silicon substrate) thioethers of 12.5mmol in 39mL octadecylene react 20min, are coated on ZnSe shell with being formed
ZnS shell obtains the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 with volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSe/ZnS quantum dot.
Comparative example 5
The preparation process of quantum dot in comparative example 5 is as follows:
(1) 120mol oleic acid, 1mol octadecylene Hybrid Heating are obtained into the first mixed liquor to 300 DEG C.And first is mixed
Liquid carries out degasification 30min, and reaction later carries out under protection of argon gas.33mmol trimethyl indium solution (is dissolved in simultaneously
In 70mL octadecylene) and 42.16mmol diethyl zinc solution (being dispersed in 70ml octadecylene) inject uniformly to the first mixed liquor
In, obtain the first reaction solution.By bis- (trimethyl silicon substrate) the thioether dispersions of (trimethylsilyl) phosphine of 31.2mmol tri- and 7.36mmol
In 16mL octadecylene, fast injection reacts 60min, obtains second containing ZnInPS quantum dot core into the first reaction solution
Reaction solution.
(2) reaction temperature is down to 150 DEG C, 666mmol zinc acetate is added, be vented 30min, be warming up to 260 DEG C, be added
640mmol selenizing diisobutyl phosphine reacts 20min, to form the ZnSe shell being coated on ZnInPS core, adds and is dispersed in
Bis- (trimethyl silicon substrate) thioethers of 375mmol in 1.17L octadecylene react 20min, are coated on ZnSe shell with being formed
ZnS shell obtains the 4th reaction solution.
(3) the 4th reaction solution is down to room temperature, the mixed solvent of the methanol and n-butanol that are then 1: 3 with volume ratio is added
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
ZnInPS/ZnSe/ZnS quantum dot.
The radius of the stratum nucleare of quantum dot obtained in difference 1~embodiment of testing example 5 and 1~comparative example of comparative example 5,
The thickness of shell, the number of plies of hypostracum, outer shell the number of plies, emission peak, half-peak breadth and quantum yield, test result such as 1 institute of table
Show.Wherein, using the radius of the stratum nucleare of model JEM-2100TEM transmissioning electric mirror test quantum dot and the thickness of shell, according to
Following formula calculates the number of plies of hypostracum and the number of plies of outer shell: the number of plies of hypostracum=(hypostracum radius-stratum nucleare radius)/every
Thickness degree, the number of plies=(outer shell radius-hypostracum radius)/every thickness degree of outer shell, herein, outer shell radius, that is, shell
The thickness of layer, every layer with a thickness of 0.23nm.Using the test quantum of model Cary Eclipse sepectrophotofluorometer instrument
The emission peak of point, using the half-peak breadth of Cary Eclipse sepectrophotofluorometer instrument test quantum dot.Using model
The quantum yield of Labsphere QEMS-2000-PL integrating sphere fluorescent quantum test system and test quantum dot.
The experimental data of quantum dot in each embodiment and comparative example of table 1
As can be seen that the shell thickness for the quantum dot that 1~embodiment of embodiment 5 is prepared is compared with comparative example 1 from upper table 1
The shell thickness of quantum dot in~comparative example 5 is thick, and the number of plies is more, so that the half-peak breadth of quantum dot is relatively narrow, quantum is produced
Rate is 70% or more, wherein the quantum yield of the quantum dot in embodiment 5 is up to 78%.And it can also from upper table 1
Out, the emission peak wavelength for the quantum dot that embodiment is prepared is adjustable from 525nm to 630nm, so as to obtain difference
The quantum dot of luminescent color.
In the experimental data for the quantum dot being prepared from embodiment 2 as can be seen that using the preparation method in embodiment 2
It can make the preparation mass production of quantum dot, and the half-peak breadth of quantum dot that volume production obtains is relatively narrow, quantum yield is higher, and not bright
Aobvious decline.And from being can be seen that in comparative example 5 using after the method mass production in comparative example 4, quantum yield is remarkably decreased, and is said
The bright preparation method using the quantum dot in convention control's example 4 can not be used for volume production.
The ultraviolet spectrogram of the ZnInPS core of quantum dot in embodiment 1 is as shown in Figure 2.ZnInPS/ in embodiment 1
The fluorescence spectra of ZnSeS/ZnS quantum dot is as shown in Figure 3.The TEM of ZnInPS/ZnSeS/ZnS quantum dot in embodiment 1 schemes
As shown in Figure 4.Wherein, it carries out ultraviolet spectra and tests the instrument used as model Cary4000 ultraviolet-uisible spectrophotometer.
It carries out fluorescence spectrum and tests the instrument used as Cary Eclipse sepectrophotofluorometer.Carry out the instrument that TEM test uses
For LabsphereQEMS-2000-PL integrating sphere fluorescent quantum test macro.
From figure 2 it can be seen that the absorption peak of the ZnInPS/ZnSeS/ZnS quantum dot in embodiment 1 is 425nm.From figure
As can be seen that the emission peak of ZnInPS/ZnSeS/ZnS quantum dot is 525nm in 3.Figure 4, it is seen that in embodiment 1
To the partial size of quantum dot be about 6nm.
Above-mentioned experimental result shows the quantum dot enabled to using the preparation method of the quantum dot in embodiment
Half-peak breadth is relatively narrow, and quantum yield is higher.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of quantum dot, which is characterized in that including stratum nucleare and shell, the component of the material of the stratum nucleare includes phosphorus member
Element, phosphide element, Zn-ef ficiency and element sulphur, the radius of the stratum nucleare are 2nm~6nm, the shell with a thickness of 8nm~16nm,
The shell includes the hypostracum being coated on the stratum nucleare and the outer shell that is coated on the hypostracum, the hypostracum
Material is selected from one of ZnSeS and ZnSe, and the material of the outer shell is ZnS.
2. quantum dot according to claim 1, which is characterized in that in the stratum nucleare, the Zn-ef ficiency and the phosphide element
Molar ratio be 1.1: 5.0~5.0: 1.1；And/or
The molar ratio of the P elements and the phosphide element is 0.1: 1.0~3.0: 1.0；And/or
The molar ratio of the element sulphur and the phosphide element is 0.1: 1.0~2.0: 1.0.
3. quantum dot according to claim 1, which is characterized in that the ratio of the radius of the thickness of the shell and the stratum nucleare
It is 1: 1~6: 1.
4. quantum dot according to claim 1, which is characterized in that the number of plies of the hypostracum is 10 layers~20 layers, described
The number of plies of outer shell is 1 layer~10 layers.
5. a kind of preparation method of quantum dot, which comprises the steps of:
First zinc source and indium source are added in the first mixed liquor, then are warming up to 100 DEG C~200 DEG C reactions, obtains the first reaction
Liquid contains ligand and non-complexing solvent in first mixed liquor；
Phosphorus source and the first sulphur source are added in first reaction solution, then are warming up to 200 DEG C~300 DEG C reactions, obtains second
Reaction solution；
At least one of selenium source and the second sulphur source are mixed with second reaction solution and the second mixed liquor, then are warming up to 250
DEG C~300 DEG C of reactions, third reaction solution is obtained, contains the second zinc source in second mixed liquor；And
Third zinc source and third sulphur source are added in the third reaction solution, then are warming up to 300 DEG C~350 DEG C reactions, is obtained
Quantum dot.
6. the preparation method of quantum dot according to claim 5, which is characterized in that described that first zinc source and indium source are added
To the step in the first mixed liquor include: by first zinc source and the indium source difference wiring solution-forming, then with 10mL/min~
The rate of 20mL/min is injected into first mixed liquor simultaneously；And/or
The step that phosphorus source and the first sulphur source are added in first reaction solution includes: by phosphorus source and described first
Sulphur source wiring solution-forming, then be injected into first reaction solution with the rate of 20mL/min~40mL/min.
7. the preparation method of quantum dot according to claim 5, which is characterized in that it is described will be in selenium source and the second sulphur source
At least one the step of mixing with second reaction solution and the second mixed liquor includes: the first speed with 10mL/min~20mL/min
Second reaction solution is injected into second mixed liquor by rate, then will be described with the rate of 0.1mL/min~2.0mL/min
At least one of selenium source and second sulphur source are injected into second mixed liquor.
8. the preparation method of quantum dot according to claim 5, which is characterized in that described by third zinc source and third sulphur source
The step being added in the third reaction solution include: by third zinc source and the third sulphur source wiring solution-forming, then with
The rate of 0.1mL/min~2.0mL/min is injected into the third reaction solution.
9. the preparation method of quantum dot according to claim 5, which is characterized in that described that first zinc source and indium source are added
Into the first mixed liquor, then in the step of being warming up to 100 DEG C~200 DEG C reactions, temperature is 130 DEG C~150 DEG C, and the reaction time is
1min~60min.
10. the preparation method of quantum dot according to claim 5, which is characterized in that described to add phosphorus source and the first sulphur source
Enter into first reaction solution, then in the step of being warming up to 200 DEG C~300 DEG C reactions, temperature is 250 DEG C~280 DEG C, reaction
Time is 10min~100min.
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| CN113554972A (en) * | 2020-04-08 | 2021-10-26 | 陈学仕 | Crosstalk improving method for QLED display panel and QLED display panel |
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