CN109971481A - Preparation method based on the cadmium-free quantum dots that epitaxial growth InP shell shines - Google Patents
Preparation method based on the cadmium-free quantum dots that epitaxial growth InP shell shines Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of cadmium-free quantum dots to be shone based on epitaxial growth InP shell, and using broad-band gap quantum dot as core, the InP shell of extension homoepitaxial narrow band gap continues the cladding of broad-band gap gradient shell as the centre of luminescence.Prepared quantum dot can obtain corresponding luminous peak position by adjusting InP shell thickness, and it is improved with relatively narrow emission spectrum, luminous efficiency and stability there has also been significant.The size of ZnSe quantum dot is distributed very uniform, half-peak width, and the dimensional homogeneity of quantum dot can not only be effectively ensured in the cladding that narrow band gap InP luminescent layer is carried out on the basis of ZnSe core, is also convenient for the thickness by controlling InP come accuracy controlling luminous peak position.Therefore, the method that epitaxial growth narrow band gap InP shell of the present invention shines and is able to maintain narrow half-peak breadth continues to coat gradient shell on the basis of indium phosphide shell, further improves the quantum yield and stability of cadmium-free quantum dots.
Description
Technical field
The present invention relates to a kind of preparation method of cadmium-free quantum dots, more particularly to it is a kind of with core-shell structure without cadmium amount
The preparation method of son point, is applied to semiconductor nano material synthesis technical field.
Background technique
Quantum dot has many unique and superior optical characteristics as a kind of novel nano material, as launch wavelength can
It adjusts, that extent of fluorescence covers ultraviolet to infrared entire spectral region, half-peak width, thermal stability is good, solution preparation cost is low etc. is excellent
Point, therefore the extensive concern by the whole world.Recently as the deep and swift and violent development of quantum dot research, in solar-electricity
There has been good application value in pond, LED illumination, photodetector, laser, bio-imaging etc..Since quantum is pointed out
Many color representations and lower preparation cost, are especially apparent in the application value of flat display field.However existing market
Quantum dot used in upper is mostly cadmium system quantum dot, contained toxic heavy-metal elements cadmium make the market development of quantum dot by
To certain limitation.Therefore developing environmental type cadmium-free quantum dots is the emphasis for still needing to research at present.
Iii-v indium phosphide (InP) semiconductor-quantum-point with its emission wavelength adjustable, low toxin by researcher
Concern, and have a wide range of applications in fields such as display, illumination, biology and solar batteries.In the prior art, about
The preparation process of InP core-shell quanta dots is more mature, obtained quantum dot property relative good.But with cadmium system quantum dot
It compares, InP quantum dot is nucleated that homogeneity is poor, size wider distribution, and the size of InP core is difficult to accuracy controlling, needs to pass through
It adulterates or to the indirect quantum point luminous peak position of the thickness control of zinc selenide/zinc sulphide (ZnSe/ZnS) shell.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Preparation method based on the cadmium-free quantum dots that epitaxial growth InP shell shines, using broad-band gap quantum dot as core, extension homoepitaxial
The InP shell of narrow band gap continues the cladding of broad-band gap gradient shell as the centre of luminescence.Prepared quantum dot can pass through tune
Section InP shell thickness obtains corresponding luminous peak position, and its with relatively narrow emission spectrum, luminous efficiency and stability, there has also been aobvious
The raising of work.
In order to achieve the above objectives, the invention uses following inventive concept:
The size distribution of ZnSe quantum dot is very uniform, and half-peak width (< 20nm) carries out narrow on the basis of ZnSe core
The dimensional homogeneity of quantum dot can not only be effectively ensured in the cladding of band gap InP luminescent layer, be also convenient for the thickness by controlling InP
Carry out accuracy controlling luminous peak position.Therefore, the present invention is shone using epitaxial growth narrow band gap InP shell and is able to maintain narrow half-peak breadth
Method, for cadmium-free quantum dots use and development has very important significance.
Conceived according to foregoing invention, the present invention adopts the following technical scheme:
A kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, is included the following steps:
The preparation of a.ZnSe core:
Prepare the precursor solution that zinc source is mixed with solvent, the precursor solution mixed using selenium source with solvent, by two kinds
Precursor solution mixing, and 140~310 DEG C are warming up to, at least heat preservation 80min reacts fully, and obtains uniform morphology and ruler
Very little ZnSe core；
The preparation of b.ZnSe@InP Core-shell structure material:
At 30~80 DEG C, indium phosphide precursor solution is added in ZnSe core to preparing in the step a, and be warming up to
260~290 DEG C of heat preservation at least 3min generate the luminous shell of InP outside ZnSe core, obtain ZnSe@InP Core-shell structure material；
C. with the cadmium-free quantum dots preparation of gradient shell cladding:
It is molten that the presoma containing zinc, sulphur, selenium is added into the ZnSe@IP kernel shell structure material prepared in the step b
Liquid, and be adjusted to 270~300 DEG C of heat preservation at least 150min and react fully, then stop heating, obtains coating with gradient shell
Without cadmium ZnSe/InP/ZnSe/ZnS quantum dot, then use n-hexane or ethanol purification quantum dot, by obtained sediment
It is dissolved in n-hexane and saves, reaction terminates.
As currently preferred technical solution, in the step c, it is described have gradient shell refer to InP shine
The outside of shell continues the external of generation and coats shell, and the thickness of the luminous shell of the InP is adjustable, passes through and adjusts the luminous shell of InP
The regulation of thickness degree has the luminous peak position of the cadmium-free quantum dots of gradient shell cladding.
As currently preferred technical solution, in the step c, the fluorescent emission peak position of the cadmium-free quantum dots exists
Between 525~560nm.
As currently preferred technical solution, in the step c, have gradient Shell Materials along on thickness direction
With InP, zinc, sulphur, selenium component gradient.The technical solution further preferred as the present invention, by 270~300 DEG C of models
Interior temperature-gradient method is enclosed, and at least adjusts the concentration of precursor solution in temperature range in each stage, realizing has gradient shell material
Material is along the component gradient on thickness direction.
As currently preferred technical solution, in the step c, the material of the gradient shell includes InP, In
(Zn) at least one of P, In (Ga) P, ZnSe, ZnSeS and ZnS；When the material of the gradient shell includes In (Ga) P,
Ga in In (Ga) P comes from gallium source, and the gallium source includes at least one of gallium chloride, gallium bromide and gallium iodide.
As currently preferred technical solution, in the step a, the zinc source is zinc acetate, zinc carbonate, sulfuric acid
At least one of zinc, zinc oleate, ten sour zinc, zinc undecylenate, zinc stearate, zinc chloride；The selenium source is selenium powder.
As currently preferred technical solution, in the step b, the indium phosphide precursor solution is by indium forerunner
Liquid solution and phosphorus precursor solution are mixed, and the indium presoma uses indium acetate, carbonic acid indium, indium nitrate, inidum chloride, bromination
At least one of indium, indium iodide, sour ligand indium compound；Wherein sour ligand uses ten acid, undecenoic acid, tetradecylic acid, 16
At least one of acid, oleic acid and stearic acid；The phosphorus presoma uses three (trimethylsilyl) phosphorus, three (trimethyl silicon substrates)
At least one of phosphorus.
As currently preferred technical solution, in the step b, in indium precursor solution and phosphorus precursor solution
The molar ratio of In and P is 6:(3~4).
It further include zinc precursor in the indium precursor solution in the step b as currently preferred technical solution
Body.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention injects the technological means of quick forming core using high warm, zinc selenide core is obtained, in the first temperature
It is lower to inject indium, phosphorus presoma into zinc selenide core and be warming up to second temperature, form the luminous shell of indium phosphide zinc.Finally in third temperature
Continue to coat broad-band gap gradient shell under degree, obtains cadmium-free quantum dots of the fluorescent emission peak position between 525nm to 560nm；
2. the method for the present invention injects quick forming core method using high warm, it is ensured that react uniformly, to obtain uniform pattern
And size；
3. the method for the present invention, as the centre of luminescence, passes through regulation thickness by the InP shell of extension homoepitaxial narrow band gap
Luminous peak position is adjusted, and continues to coat gradient shell on this basis, electrons and holes can be limited at luminous shell
Compound luminous efficiency and stability to improve quantum dot, to realize the preparation without cadmium ZnSe/InP/ZnSe/ZnS quantum dot.
Above-mentioned design scheme provides a kind of new method and thinking for the preparation of high quality cadmium-free quantum dots.
Detailed description of the invention
Fig. 1 is the ultraviolet-ray visible absorbing and fluorescence emission spectrum of cadmium-free quantum dots sample 1 prepared by the embodiment of the present invention one
Figure.
Fig. 2 is the ultraviolet-ray visible absorbing and fluorescence emission spectrum of cadmium-free quantum dots sample 2 prepared by the embodiment of the present invention two
Figure.
Fig. 3 is the ultraviolet-ray visible absorbing and fluorescence emission spectrum of cadmium-free quantum dots sample 3 prepared by the embodiment of the present invention three
Figure.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
The reaction process of the following embodiments of the present invention carries out under the protection of atmosphere of inert gases.Wherein inert gas packet
Include nitrogen, at least one of argon gas or rare gas.
In order to solve the problems, such as the indium phosphide quantum dot for obtaining narrow emission spectrum more difficult at present, the invention discloses a kind of nothings
The preparation method of cadmium quantum dot, comprising the following steps:
A, zinc source and solvent mixing, heating remove water oxygen and are reacted, and obtain the zinc selenide core of uniform morphology and size；
B, indium phosphide precursor solution is added into zinc selenide core at the first temperature and is warming up to second temperature, forms phosphorus
Change the luminous shell of indium；
C, zinc, sulphur, selenium precursor solution are added on this basis and is adjusted to third temperature, and being formed has gradient shell packet
The cadmium-free quantum dots covered.
In view of InP quantum dot is nucleated, homogeneity difference causes half-peak breadth wider and outer shell thickness low LCL leads to phosphatization
The problem of indium stability difference, according to the present invention following embodiments, it is also necessary to the thickness of accurate control InP shell, and it is carried out
Multiple gradient core shell cladding.Following embodiments according to the present invention further comprise the process for separating and purifying to end reaction solution.
Reaction solution is cooled to room temperature, extractant is added, centrifugation obtains the cadmium-free quantum dots of high-purity and is dissolved in coordinative solvent.
Embodiment one:
In the present embodiment, a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, is prepared glimmering
Light emitting peak is the cadmium-free quantum dots sample 1 of 560nm, is included the following steps:
(1) preparation of zinc oleate (Zn-OA):
Zinc oxide, oleic acid and 1- octadecylene are added in three-necked flask, is passed through nitrogen, is heated to dissolving, is dropped after reacting 1h
To room temperature, zinc oleate (Zn-OA) clear transparent solutions that concentration is 0.4M are obtained；
(2) preparation of selenium-tri octyl phosphine (Se-TOP):
In a nitrogen environment, elemental selenium and tri octyl phosphine are mixed and is made it dissolve, it is molten to obtain the Se-TOP that concentration is 2M
Liquid；
(3) hexadecylic acid-indium (In (PA)3) preparation:
In a nitrogen environment, by 0.15mmol indium acetate, 0.45mmol hexadecylic acid, 0.05mmol zinc stearate and 10mL
1- octadecylene is mixed, and is passed through nitrogen and is down to room temperature after being heated to 120 DEG C of holding 1h, obtains hexadecylic acid-indium (In
(PA)3)；
(4) preparation of selenium powder-octadecylene (SUS-Se) suspension:
In air environment, the selenium powder of 0.4mmol and the octadecylene of 3mL are added in sample bottle, uses supersonic wave cleaning machine
It is thoroughly dispersed in selenium powder in octadecylene, obtains selenium powder-octadecylene (SUS-Se) suspension；
(5) preparation of ZnSe core:
0.8mmol zinc stearate and 15mL paraffin oil are added in three-necked flask, is passed through nitrogen, is warming up to 140 DEG C and takes out very
Empty 20min；It is warming up to 310 DEG C later, the fast injection 0.4mmol SUS-Se into reaction is obtained in 310 DEG C of heat preservation 1h
The ZnSe core of one morphology and size；
(6) prepared by ZnSe@InP Core-shell structure material:
60 DEG C will be cooled to equipped with the three-neck flask for preparing ZnSe core in the step (5), and 0.15mmol ten is added
Six acid-indium maintains 20min, is down to room temperature later and 0.1mmol tri- (trimethyl silicon substrate) phosphine is slowly added dropwise, be brought rapidly up to 290
DEG C and keep 3min, outside ZnSe core generate InP shine shell, obtain ZnSe@InP Core-shell structure material；
(7) with the cadmium-free quantum dots preparation of gradient shell cladding:
3mmol zinc stearate is added into the ZnSe@InP Core-shell structure material prepared in the step (6), and slowly
3mmol Se-TOP is added；270 DEG C are then cooled the temperature to, 2mmol Zn-OA and 2mmol 1- lauryl mercaptan, heat preservation is added
After 30min, 280 DEG C are warming up to, continuously adds 2mmol Zn-OA and 2mmol 1- lauryl mercaptan, is warming up to after keeping the temperature 30min
290 DEG C, 2mmol Zn-OA and 2mmol 1- lauryl mercaptan is added, 300 DEG C is warming up to after keeping the temperature 30min, stops after keeping the temperature 1h
Heating；Obtain having gradient shell coats without cadmium ZnSe/InP/ZnSe/ZnS quantum dot, it is then pure using n-hexane or ethyl alcohol
Change quantum dot, obtained sediment is dissolved in n-hexane and is saved, reaction terminates.
Experimental test and analysis:
Through calculating, the quantum yield of cadmium-free quantum dots sample 1 prepared by the present embodiment is 45%.
Fig. 1 is the fluorescence emission spectrogram of compound of the cadmium-free quantum dots sample 1 prepared in embodiment one, as can be seen from Figure 1 its
Fluorescent emission peak value is 560nm, half-peak breadth 55nm.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, is prepared glimmering
Light emitting peak is the cadmium-free quantum dots sample 2 of 542nm, is included the following steps:
(1) preparation of zinc oleate (Zn-OA): this step is the same as example 1；
(2) preparation of selenium-tri octyl phosphine (Se-TOP): this step is the same as example 1；
(3) hexadecylic acid-indium (In (PA)3) preparation: this step is the same as example 1；
(4) preparation of selenium powder-octadecylene (SUS-Se) suspension: this step is the same as example 1；
(5) preparation of ZnSe core: this step is the same as example 1；
(6) prepared by ZnSe@InP Core-shell structure material:
60 DEG C will be cooled to equipped with the three-neck flask for preparing ZnSe core in the step (5), and 0.12mmol ten is added
Six acid-indium maintains 20min, is down to room temperature later and 0.08mmol tri- (trimethyl silicon substrate) phosphine is slowly added dropwise, be brought rapidly up to 290
DEG C and keep 3min, outside ZnSe core generate InP shine shell, obtain ZnSe@InP Core-shell structure material；
(7) with the cadmium-free quantum dots preparation of gradient shell cladding: this step is the same as example 1.
Experimental test and analysis:
Through calculating, the quantum yield of cadmium-free quantum dots sample 2 prepared by the present embodiment is 55%.
Fig. 1 is the fluorescence emission spectrogram of compound of the cadmium-free quantum dots sample 2 prepared in embodiment two, as can be seen from Figure 2 its
Fluorescent emission peak value is 542nm, half-peak breadth 50nm.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, is prepared glimmering
Light emitting peak is the cadmium-free quantum dots sample 3 of 530nm, is included the following steps:
(1) preparation of zinc oleate (Zn-OA): this step is the same as example 1；
(2) preparation of selenium-tri octyl phosphine (Se-TOP): this step is the same as example 1；
(3) hexadecylic acid-indium (In (PA)3) preparation: this step is the same as example 1；
(4) preparation of selenium powder-octadecylene (SUS-Se) suspension: this step is the same as example 1；
(5) preparation of ZnSe core: this step is the same as example 1；
(6) prepared by ZnSe@InP Core-shell structure material:
60 DEG C will be cooled to equipped with the three-neck flask for preparing ZnSe core in the step (5), and 0.1mmol 16 is added
Acid-indium maintains 20min, is down to room temperature later and 0.05mmol tri- (trimethyl silicon substrate) phosphine is slowly added dropwise, be brought rapidly up to 290 DEG C
And 3min is kept, the luminous shell of InP is generated outside ZnSe core, obtains ZnSe@InP Core-shell structure material；
(7) with the cadmium-free quantum dots preparation of gradient shell cladding: this step is the same as example 1.
Experimental test and analysis:
Through calculating, the quantum yield of cadmium-free quantum dots sample 3 prepared by the present embodiment is 62%.
Fig. 1 is the fluorescence emission spectrogram of compound of the cadmium-free quantum dots sample 3 prepared in embodiment three, as can be seen from Figure 3 its
Fluorescent emission peak value is 530nm, half-peak breadth 45nm.The cadmium-free quantum dots that the present embodiment is shone based on epitaxial growth InP shell
Preparation method, at least adjust presoma by the temperature-gradient method within the scope of 270~300 DEG C, and in each stage in temperature range
The concentration of solution, realizing has gradient Shell Materials along the component gradient on thickness direction.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, including such as
Lower step:
(1) preparation of zinc oleate (Zn-OA): this step is the same as example 1；
(2) preparation of selenium-tri octyl phosphine (Se-TOP): this step is the same as example 1；
(3) hexadecylic acid-indium (In (PA)3) preparation: this step is the same as example 1；
(4) preparation of selenium powder-octadecylene (SUS-Se) suspension: this step is the same as example 1；
(5) preparation of ZnSe core: this step is the same as example 1；
(6) prepared by ZnSe@InP Core-shell structure material:
60 DEG C will be cooled to equipped with the three-neck flask for preparing ZnSe core in the step (5), and 0.1mmol 16 is added
Acid-indium maintains 20min, is down to room temperature later and 0.05mmol tri- (trimethyl silicon substrate) phosphine is slowly added dropwise, indium phosphide forerunner is made
Liquid solution further includes zinc precursor 0.1mmol zinc stearate in indium precursor solution, is brought rapidly up to 290 DEG C and keeps 3min,
The luminous shell of InP is generated outside ZnSe core, obtains ZnSe@InP Core-shell structure material；
(7) with the cadmium-free quantum dots preparation of gradient shell cladding: this step is the same as example 1.
Experimental test and analysis:
Through calculating, the quantum yield of cadmium-free quantum dots sample 4 prepared by the present embodiment is 65%.
According to the fluorescence emission spectrum analysis of the cadmium-free quantum dots sample 3 prepared in example IV, it is known that its fluorescent emission
Peak value is 525nm, half-peak breadth 43nm.The preparation side for the cadmium-free quantum dots that the present embodiment is shone based on epitaxial growth InP shell
Method by the temperature-gradient method within the scope of 270~300 DEG C, and at least adjusts the dense of precursor solution in each stage in temperature range
It spends, further includes zinc precursor 0.8mmol zinc stearate in indium precursor solution, realizing has gradient Shell Materials along thickness side
Upward component gradient obtains no cadmium ZnSe/InP/ZnSe/ZnS quanta point material.The present embodiment is quick using high warm injection
Forming core method, it is ensured that reaction is uniform, to obtain uniform morphology and size.And pass through the InP shell of extension homoepitaxial narrow band gap
Layer is used as the centre of luminescence, adjusts luminous peak position by regulation thickness, and continue to coat gradient shell on this basis, can will
Electrons and holes are limited in compound luminous efficiency and stability to improve quantum dot at luminous shell.
Embodiment five:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, the tool
Have gradient shell refer to InP shine shell outside continue to generate it is external coat shell, the InP shines the thickness of shell
Luminous peak position adjustable, that there are the cadmium-free quantum dots of gradient shell cladding by adjusting the luminous shell thickness regulation of InP.The present invention
Method can satisfy diversified demand, need custom materials product according to function.
By the data in comparison above embodiments it can be found that the present invention grows indium phosphide hair on the basis of ZnSe core
Bare hull layer realizes narrow emission spectrum.And continue to coat gradient shell on the basis of indium phosphide shell, further improve no cadmium amount
The quantum yield and stability of son point.To sum up, the present invention provides a kind of preparation methods of cadmium-free quantum dots, to a certain extent
It solves the problems, such as that the prior art is difficult to obtain narrow emission spectrum cadmium-free quantum dots, is provided for preparation high quality cadmium-free quantum dots
A kind of new method and thinking.In addition, cadmium-free quantum dots optical property relative good prepared by the present invention, toxicity is low, synthesizes
Method is simple, is illuminating, display, and the fields such as biology have good development prospect.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Utilize ionic liquid pretreatment coal for being electrolysed the technical principle and inventive concept of liquefied method without departing from the present invention,
Belong to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the cadmium-free quantum dots to be shone based on epitaxial growth InP shell, which is characterized in that including walking as follows
It is rapid:
The preparation of a.ZnSe core:
Prepare the precursor solution that zinc source is mixed with solvent, the precursor solution mixed using selenium source with solvent, by two kinds of forerunners
Liquid solution mixing, and is warming up to 140~310 DEG C, and at least heat preservation 80min reacts fully, and obtains uniform morphology and size
ZnSe core；
The preparation of b.ZnSe@InP Core-shell structure material:
At 30~80 DEG C, indium phosphide precursor solution is added in ZnSe core to preparing in the step a, and be warming up to 260
~290 DEG C of heat preservation at least 3min generate the luminous shell of InP outside ZnSe core, obtain ZnSe@InP Core-shell structure material；
C. with the cadmium-free quantum dots preparation of gradient shell cladding:
Into the ZnSe@InP Core-shell structure material prepared in the step b be added containing zinc, sulphur, selenium precursor solution,
And be adjusted to 270~300 DEG C of heat preservation at least 150min and react fully, then stop heating, obtains that there is gradient shell cladding
Without cadmium ZnSe/InP/ZnSe/ZnS quantum dot, n-hexane or ethanol purification quantum dot are then used, obtained sediment is molten
Solution saves in n-hexane, and reaction terminates.
2. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step c, it is described with gradient shell refer to InP shine shell outside continue generate external encasement
The thickness of layer, the luminous shell of the InP is adjustable, the nothing that by adjusting the luminous shell thickness regulation of InP there is gradient shell to coat
The luminous peak position of cadmium quantum dot.
3. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step c, the fluorescent emission peak position of the cadmium-free quantum dots is between 525~560nm.
4. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step c, with gradient Shell Materials along the component gradient on thickness direction with InP, zinc, sulphur, selenium.
5. the preparation method of the cadmium-free quantum dots to be shone according to claim 4 based on epitaxial growth InP shell, feature are existed
In: in the step c, at least adjusted by the temperature-gradient method within the scope of 270~300 DEG C, and in each stage in temperature range
The concentration of precursor solution, realizing has gradient Shell Materials along the component gradient on thickness direction.
6. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step c, the material of the gradient shell includes in InP, In (Zn) P, In (Ga) P, ZnSe, ZnSeS and ZnS
At least one；When the material of the gradient shell includes In (Ga) P, the Ga in In (Ga) P comes from gallium source, the gallium source packet
Include at least one of gallium chloride, gallium bromide and gallium iodide.
7. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step a, the zinc source is zinc acetate, zinc carbonate, zinc sulfate, zinc oleate, ten sour zinc, zinc undecylenate, tristearin
At least one of sour zinc, zinc chloride, zinc stearate；The selenium source is selenium powder.
8. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step b, the indium phosphide precursor solution is mixed by indium precursor solution and phosphorus precursor solution,
The indium presoma is using in indium acetate, carbonic acid indium, indium nitrate, inidum chloride, indium bromide, indium iodide, sour ligand indium compound
It is at least one；Wherein sour ligand is using at least one of ten acid, undecenoic acid, tetradecylic acid, hexadecylic acid, oleic acid and stearic acid；
The phosphorus presoma uses at least one of three (trimethylsilyl) phosphorus, three (trimethyl silicon substrate) phosphorus.
9. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature are existed
In: in the step b, the molar ratio of indium precursor solution and In and P in phosphorus precursor solution are 6:(3~4).
10. the preparation method of the cadmium-free quantum dots to be shone according to claim 1 based on epitaxial growth InP shell, feature
It is: further includes zinc precursor in the indium precursor solution in the step b.
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