CN108269891A - A kind of nanocomposite, preparation method and semiconductor devices - Google Patents

A kind of nanocomposite, preparation method and semiconductor devices Download PDF

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Publication number
CN108269891A
CN108269891A CN201611259353.9A CN201611259353A CN108269891A CN 108269891 A CN108269891 A CN 108269891A CN 201611259353 A CN201611259353 A CN 201611259353A CN 108269891 A CN108269891 A CN 108269891A
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presoma
nanocomposite
cadmium
preparation
zinc
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CN108269891B (en
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杨行
杨一行
刘政
钱磊
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TCL Corp
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TCL Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region

Abstract

The present invention discloses a kind of nanocomposite, preparation method and semiconductor devices, and method includes step：Pre-position adds in one or more kinds of cationic presomas in radial directions；Add in one or more kinds of anion presomas simultaneously under certain condition, cationic presoma is made react forming nanocomposite with anion presoma, and there is blue shift, red shift and one or more of constant during the reaction in the glow peak wavelength of the nanocomposite, is distributed so as to fulfill in the alloy compositions of pre-position.Pass through the nanocomposite prepared by above-mentioned preparation method, not only realize more efficient nanocomposite luminous efficiency, it also can more meet the comprehensive performance requirement of semiconductor devices and corresponding display technology to nanocomposite simultaneously, be a kind of suitable semiconductor devices and the preferable quantum dot luminescent material of display technology.

Description

A kind of nanocomposite, preparation method and semiconductor devices
Technical field
The present invention relates to a kind of quantum dot field more particularly to nanocomposite, preparation method and semiconductor devices.
Background technology
Quantum dot is a kind of special material for being limited in nanometer scale in three dimensions, this significant Quantum confined effect causes quantum dot to be provided with many unique nanometer properties：Launch wavelength is continuously adjusted, emission wavelength is narrow, is inhaled Receive spectral width, luminous intensity height, fluorescence lifetime length and good biocompatibility etc..These features cause quantum dot to be shown in tablet Show, the fields such as solid-state lighting, photovoltaic solar, biomarker are respectively provided with the prospect of being widely applied.It especially should in FPD With aspect, the quanta point electroluminescent diode component based on quanta point material（Quantum dot light-emitting Diodes, QLED）Characteristic and optimization by means of CdS quantum dots, in display image quality, device performance, manufacture cost Etc. shown huge potentiality.Although the performance of QLED devices in all respects is continuously available promotion in recent years no matter It is also to have phase with the requirement of commercial application in device efficiency or in the basic devices performance parameter such as device job stability When gap, this also hinders the development and application of quanta point electroluminescent display technology significantly.In addition, it is not limited only to QLED devices Part, in other areas, quanta point material are also gradually paid attention to relative to the characteristic of traditional material, such as photo luminescent devices, Solar cell, display device, photodetector, bioprobe and device for non-linear optical etc., below only with QLED devices It is illustrated for part.
Although quantum dot has been studied and developed more than 30 years as a kind of nano material of classics, quantum is utilized The superior luminescence characteristics of point simultaneously apply grinding in QLED devices and corresponding display technology as quantum dot composite material It is also very short to study carefully the time；Therefore the R and D of the QLED devices of the overwhelming majority at present are all based on having classical architecture system Quanta point material, the standard of screening and the optimization of corresponding quanta point material is also substantially from the luminescent properties example of quantum dot itself The luminous peak width of such as quantum dot, solution quantum yield set out.By more than quantum dot directly apply in QLED device architectures from And obtain corresponding device performance result.
But the photoelectric device system of QLED devices and corresponding display technology as a set of complexity, have it is all it is various because Element can influence the performance of device.List is from the quanta point material as core emitting layer material, the quantum dot of required tradeoff Energy index will be much more complex.
First, quantum dot is existing in the form of quantum dot light emitting layer solid film in QLED devices, therefore quantum Originally obtained every luminescent properties parameter can show apparent difference to point material after solid film is formed in the solution： Such as glow peak wavelength has different degrees of red shift in solid film（It is moved to long wavelength）, shine peak width can become larger, Quantum yield has different degrees of reduction, that is to say, that the superior luminescence performance of quanta point material in the solution can not be complete It is inherited into the quantum dot solid film of QLED devices.Therefore in the structure and synthesizing formula for designing and optimizing quanta point material When, the hair of the luminescent properties optimization and quanta point material of quanta point material itself under solid film state need to be considered simultaneously Optical property, which is inherited, to be maximized.
Secondly, the luminous of quanta point material is realized by electroexcitation in QLED devices, i.e., respectively from QLED Anode and cathodal closing the injection hole of device and electronics, hole and electronics are existed by the transmission of corresponding function layer in QLED devices After quantum dot light emitting layer is compound, emitted by way of radiation transistion photon realize shine.From above procedure as can be seen that amount It is to influence the efficiency of radiation transistion in the above process that son, which puts the luminescent properties of itself such as luminous efficiency, and QLED devices is whole Body luminous efficiency can also simultaneously by hole in the above process and electronics in quanta point material charge injection and efficiency of transmission, Relative charge balance in quanta point material of hole and electronics, the recombination region of hole and electronics in quanta point material etc. It influences.Therefore when designing and optimizing the fine nanometer nuclear shell nano-structure of structure especially quantum dot of quanta point material, weight is also needed Point considers that quantum dot forms the later electric property of solid film：Such as the charge of quantum dot injects and conductive performance, quantum dot Fine band structure, quantum dot exciton lifetime etc..
Finally, it is contemplated that QLED devices and corresponding display technology future will pass through the solution rule of great production cost advantage If prepared by ink-jet printing, therefore the design of material of quantum dot and exploitation need to consider the processing performance of quantum dot solution, Such as the dispersible dissolubility of quantum dot solution or marking ink, colloidal stability, it is printed as film property etc..Meanwhile quantum dot material The exploitation of material will also be cooperateed with the whole preparation process flow and requirement of other functional layer materials of QLED devices and device.
In short, traditional only being designed from the quantum-dot structure for promoting quantum dot itself luminescent properties consideration is can not to expire Sufficient QLED devices and corresponding display technology are various in optical property, electric property, processing performance etc. for quanta point material Composite request.The requirement for QLED devices and corresponding display technology is needed, to the fine of quantum dot quantum point composite material Nucleocapsid, component, energy level etc. carry out customized.
Due to the high surface atom ratio of quantum dot, not with surface ligand（Ligand）Form non-covalent bond（Dangling bond）Atom will exist with surface defect state, this surface defect state will cause the transition of non-radiative pathway so that The photoluminescence quantum yield of quantum dot is substantially lowered.To solve this problem, it can grow and include in former quantum dot superficies The semiconductor shell of another semi-conducting material forms the nucleocapsid of quantum dot（core-shell）Structure, can the amount of significantly improving The luminescent properties of son point, while increase the stability of quantum dot.
Can be applied to the quanta point material of high-performance QLED devices exploitation predominantly has the quantum dot of nucleocapsid, Fixed and nucleocapsid has clear and definite boundary respectively for core and shell component.Such as quantum dot (the J. with CdSe/ZnS nucleocapsids Phys. Chem., 1996,100 (2), 468-471), there is quantum dot (the J. Am. of CdSe/CdS nucleocapsids Chem. Soc. 1997,119, (30), 7019-7029), the quantum dot with CdS/ZnS nucleocapsids, with CdS/ The quantum dot (7,919,012 B2 of Patent US) of CdSe/CdS cores+multilayer shell structurre, have CdSe/CdS/ZnS cores+ Quantum dot (J. Phys. Chem. B, 2004,108 (49), 18826-18831) of multilayer shell structurre etc..At these In the quantum dot of nucleocapsid, usually the constituent of core and shell is fixed and different, and is usually by a kind of sun The binary compound system of ion and a kind of anion composition.In this configuration, since the growth of core and shell is independent difference It carries out, therefore the boundary between core and shell is clear and definite, i.e., core and shell can be distinguished.The exploitation of this nuclear shell structure quantum point Greatly improve luminous quantum efficiency, monodispersity and the quantum dot stability of original single component quantum dot.
Although the quantum dot part of nucleocapsid described above improves quantum dot performance, from mentality of designing or From prioritization scheme or from the aspect of the luminous efficiency based on promotion quantum dot itself, and luminescent properties need to be improved, In addition other aspect particular/special requirements of semiconductor devices for quanta point material are not considered yet.
Therefore, above-mentioned technology has yet to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of nanocomposite, preparation methods And semiconductor devices, it is intended to which quanta point material its luminescent properties for solving prepared by existing preparation method are to be improved, can not meet The problem of requirement of the semiconductor devices for nanocomposite.
Technical scheme is as follows：
A kind of preparation method of nanocomposite, wherein, including step：
Pre-position adds in one or more kinds of cationic presomas in radial directions；It adds in simultaneously under certain condition One or more kinds of anion presomas, make cationic presoma with anion presoma react to be formed it is nano combined Material, and the glow peak wavelength of the nanocomposite occur during the reaction blue shift, red shift and it is constant in one kind Or it is several, it is distributed so as to fulfill in the alloy compositions of pre-position.
The preparation method of the nanocomposite, wherein, in radial directions pre-position add in it is a kind of sun from Sub- presoma；It adds in two kinds of anion presomas with differential responses activity simultaneously under certain condition, makes cationic forerunner Body react forming nanocomposite with anion presoma, and the glow peak wavelength of the nanocomposite is anti- Should during blue shift, red shift and one or more of constant occur, be distributed so as to fulfill in the alloy compositions of pre-position.
The preparation method of the nanocomposite, wherein, pre-position adds in two kinds and has in radial directions The cationic presoma of differential responses activity；A kind of anion presoma is added in simultaneously under certain condition, makes cationic forerunner Body react forming nanocomposite with anion presoma, and the glow peak wavelength of the nanocomposite is anti- Should during blue shift, red shift and one or more of constant occur, be distributed so as to fulfill in the alloy compositions of pre-position.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occurs continuous blue shift in the process.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occurs alternate blue shift and constant in the process.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occur alternate blue shift and red shift in the process.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occurs the blue shift being interrupted in the process.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occurs the red shift being interrupted in the process.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting First occur blue shift in the process, it is then constant.
The preparation method of the nanocomposite, wherein, the glow peak wavelength of the nanocomposite is reacting Occurs continuous red shift in the process.
The preparation method of the nanocomposite, wherein, the cation presoma includes the presoma of Zn, described The presoma of Zn for zinc methide, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, At least one of zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate or zinc sulfate.
The preparation method of the nanocomposite, wherein, the cation presoma includes the presoma of Cd, described The presoma of Cd for dimethyl cadmium, diethyl cadmium, cadmium acetate, acetylacetone,2,4-pentanedione cadmium, cadmium iodide, cadmium bromide, caddy, cadmium fluoride, At least one of cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate or cadmium sulfate.
The preparation method of the nanocomposite, wherein, add in one or more simultaneously in a heated condition Anion presoma.
The preparation method of the nanocomposite, wherein, the anion presoma includes the presoma of Se, described The presoma of Se is in Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA At least one.
The preparation method of the nanocomposite, wherein, the anion presoma includes the presoma of S, the S Presoma in S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide It is at least one.
The preparation method of the nanocomposite, wherein, the anion presoma includes the presoma of Te, described The presoma of Te is in Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA At least one.
The preparation method of the nanocomposite, wherein, heating temperature is between 100 DEG C to 400 DEG C.
The preparation method of the nanocomposite, wherein, heating time is in 2s between for 24 hours.
The preparation method of the nanocomposite, wherein, mole throwing of cationic presoma and anion presoma Material is than being 100:1 to 1:Between 50.
A kind of nanocomposite, wherein, the nanocomposite is prepared using as above any preparation method It forms.
A kind of semiconductor devices, wherein, including nanocomposite as described above.
The semiconductor devices, wherein, the semiconductor devices is electroluminescent device, photo luminescent devices, the sun Can be in battery, display device, photodetector, bioprobe and device for non-linear optical any one.
Advantageous effect：Nanocomposite of the present invention prepared by by above-mentioned preparation method, not only realizes more efficient Nanocomposite luminous efficiency, while also can more meet semiconductor devices and corresponding display technology to nanocomposite Comprehensive performance requirement, is a kind of suitable semiconductor devices and the preferable quantum dot luminescent material of display technology.
Description of the drawings
Fig. 1 is a kind of level structure curve of nanocomposite concrete structure 1 of the present invention.
Fig. 2 is a kind of level structure curve of nanocomposite concrete structure 2 of the present invention.
Fig. 3 is a kind of level structure curve of nanocomposite concrete structure 3 of the present invention.
Fig. 4 is a kind of level structure curve of nanocomposite concrete structure 4 of the present invention.
Fig. 5 is a kind of level structure curve of nanocomposite concrete structure 5 of the present invention.
Fig. 6 is a kind of level structure curve of nanocomposite concrete structure 6 of the present invention.
Fig. 7 is a kind of level structure curve of nanocomposite concrete structure 7 of the present invention.
Fig. 8 is the glow peak wavelength graph of quantum dot described in the embodiment of the present invention 10.
Fig. 9 is the glow peak wavelength graph of quantum dot described in the embodiment of the present invention 11.
Figure 10 is the glow peak wavelength graph of quantum dot described in the embodiment of the present invention 12.
Figure 11 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 33.
Figure 12 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 34.
Figure 13 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 35.
Figure 14 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 36.
Figure 15 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 37.
Figure 16 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 38.
Specific embodiment
The present invention provide a kind of nanocomposite, preparation method and and semiconductor devices, to make the purpose of the present invention, skill Art scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that tool described herein Body embodiment is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of preparation method of nanocomposite, including step：Precalculated position in radial directions Place adds in one or more kinds of cationic presomas；Before adding in one or more kinds of anion simultaneously under certain condition Body is driven, cationic presoma is made react forming nanocomposite with anion presoma, and the nano combined material There is blue shift, red shift and one or more of constant during the reaction in the glow peak wavelength of material, so as to fulfill being pre-positioned Put the alloy compositions distribution at place.
Preferably, pre-position adds in a kind of cationic presoma in radial directions；Add simultaneously under certain condition Enter two kinds of anion presomas with differential responses activity, cationic presoma is made to carry out reacting formation with anion presoma Nanocomposite, and there is blue shift, red shift and constant during the reaction in the glow peak wavelength of the nanocomposite One or more of, it is distributed so as to fulfill in the alloy compositions of pre-position.
Preferably, pre-position adds in two kinds of cationic presomas with differential responses activity in radial directions； A kind of anion presoma is added in simultaneously under certain condition, cationic presoma is made to carry out reacting formation with anion presoma Nanocomposite, and there is blue shift, red shift and constant during the reaction in the glow peak wavelength of the nanocomposite One or more of, it is distributed so as to fulfill in the alloy compositions of pre-position.
The present invention adds in the cationic presoma and the moon of required synthesis alloy compositions by directly controlling in pre-position Ion presoma carries out reaction and forms nanocomposite, is distributed so as to fulfill alloy compositions needed for the present invention.Its reaction principle It is that the high cationic presoma of reactivity and anion presoma first react, forms the first compound, reactivity It reacts after low cationic presoma and anion presoma, forms second of compound, and during the reaction, first It reacts afterwards and cation exchange reaction occurs between two kinds of compounds of formation, be distributed so as to fulfill alloy compositions needed for the present invention.
Described the first compound and second of compound can be binary or binary more than compound.
The preparation-obtained nanocomposite of the present invention, including at least one quantum arranged successively in radial directions Point structural unit, graded alloy component structure or radial direction of the quantum-dot structure unit for the variation of level width in the radial direction The consistent homogeneous components structure of level width on direction.
That is in the nanocomposite that prepared by the present invention, from the inside to the outside along diameter inside each quantum-dot structure unit It is with alloy compositions in the range of one layer of monoatomic layer or one layer or more of monoatomic layer in any position on direction Structure.
Further, in the present invention, the quantum-dot structure unit includes II races and VI races element.The II races element packet It includes but is not limited to Zn, Cd, Hg, Cn etc.；VI races element includes but not limited to O, S, Se, Te, Po, Lv etc..Specifically, each The alloy compositions composition of quantum-dot structure unit is CdxZn1-xSeyS1-y, wherein 0≤x≤1,0≤y≤1, and x and y differences When be 0 and be asynchronously 1.It should be noted that the above situation is preferable case, for the quantum dot knot of graded alloy component structure For structure unit, component is alloy compositions；And for the quantum-dot structure unit of homogeneous components structure, component can To be alloy compositions or non-alloyed component, but currently preferred is alloy compositions, i.e., described homogeneous components structure is Uniform alloy compositions structure, it is further preferred that comprising II races and VI races element, subsequent embodiment of the present invention is with uniform alloy group It is illustrated for separation structure, it will be clear that can equally implement for unalloyed homogeneous components structure.
Radial direction herein refers to the center outwardly direction from nanocomposite, it is assumed for example that nanometer of the invention Composite material is spherical or similar spherical structure, then the radial direction refers to the direction along radius, in nanocomposite The heart（It is or internal）Refer to the center of its physical arrangement, the surface of nanocomposite（It is or external）Refer to the table of its physical arrangement Face.
Structure existing for nanocomposite of the present invention is described in detail below：
Specifically, there is continuous blue shift during the reaction in the glow peak wavelength of the nanocomposite, to realize specified Graded alloy component distribution at position.There is blue shift and represent glow peak to the movement of shortwave direction, level width broadens, such as Fig. 1 Shown, in quantum dot in the radial direction, the level width of quantum-dot structure unit broadens（Continuous blue shift）.
Specifically, as shown in Figure 1, a kind of nanocomposite with funnel type level structure is prepared in the present invention, Quantum-dot structure unit alloy constituent inside the nanocomposite corresponds to level width and is less than positioned at outside Quantum-dot structure unit alloy constituent correspond to level width；Specifically, nanocomposite packet provided by the invention At least one quantum-dot structure unit arranged successively in radial directions is included, the quantum-dot structure unit is in the radial direction The wider graded alloy component structure of more outside level width, and the amount of graded alloy component structure adjacent in radial directions The energy level of son point structural unit is continuous；The structure of nanocomposite shown in Fig. 1 is known as specific knot in subsequent embodiment Structure 1.Nanocomposite in Fig. 1, the level width of each adjacent quantum-dot structure unit has continuous structure, i.e., each The level width of adjacent quantum-dot structure unit has the characteristics that consecutive variations rather than mutation structure, that is to say, that quantum dot Alloy compositions be also with continuity, subsequent continuous structure principle is identical.
Further, in radial directions in adjacent quantum-dot structure unit, by paracentral quantum-dot structure unit Level width is less than the level width of deep quantum-dot structure unit；That is, in the nanocomposite, It gradually broadens from the level width of center to face, it is therein to open so as to form the funnel type structure that opening becomes larger Mouth, which becomes larger, to be referred in level structure as shown in Figure 1, the energy from nanocomposite center to nanocomposite surface Grade is continuous.Meanwhile the nanocomposite in the present invention, the energy level of each adjacent quantum-dot structure unit is continuous , that is to say, that the synthesis component of quantum dot also has the characteristic of consecutive variations, and this characteristic is more advantageous to realizing high shine Efficiency.
That is, the concrete structure 1 of the nanocomposite is with radially continuous from inside to outside The quantum-dot structure of graded alloy component；This quantum-dot structure has radially continuous from inside to outside in constituent The characteristics of variation；Correspondingly, energy level distribution on also on there are from inside to outside radially consecutive variations；This amount Son point structure in constituent and the characteristics of consecutive variations in energy level distribution, relative to the quantum dot core with clear and definite boundary and The relationship of shell, nanocomposite of the invention not only contribute to realize more efficient luminous efficiency, while also can more meet half The comprehensive performance requirement of conductor device and corresponding display technology to nanocomposite, is a kind of suitable semiconductor devices and display The preferable quantum dot luminescent material of technology.
Further, in the nanocomposite provided such as Fig. 1, the alloy compositions of A points are Cdx0 AZn1-x0 ASey0 AS1-y0 A, The alloy compositions of B points are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points relative to B points closer to nanocomposite center, and A The composition of point and B points meets：x0 A>x0 B,y0 A >y0 B.That is, for any two points A points and B points in nanocomposite, And A points relative to B points closer to nanocomposite center, thenx0 A>x0 B,y0 A >y0 B, i.e. the Cd contents of A points are more than B points Cd contents, the Zn contents of A points are less than the Zn contents of B points, and the Se contents of A points are more than the Se contents of B points, and the S contents of A points are less than B The S contents of point.In this way, in the nanocomposite, grading structure is just formd in radial directions, and due to radially It is more outside on direction（I.e. far from nanocomposite center）Then Cd and Se contents are lower, Zn and S contents are higher, then according to The characteristic of these types of element, level width will be wider.
In the nanocomposite of follow-up difference concrete structure, if quantum-dot structure unit is in the radial direction more to external enwergy The wider graded alloy component structure of level width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, wherein, the conjunction of A points Golden component is Cdx0 AZn1-x0 ASey0 AS1-y0 A, the alloy compositions of B points are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points are relative to B points Closer to nanocomposite center, and the composition of A points and B points meets：x0 A>x0 B,y0 A >y0 B.If quantum-dot structure unit is diameter The narrower graded alloy component structure of more outside level width on direction, then its alloy compositions be both preferably Cdx0Zn1- x0Sey0S1-y0, wherein, the alloy compositions of C points are Cdx0 CZn1-x0 CSey0 CS1-y0 C, the alloy compositions of D points are Cdx0 DZn1- x0 DSey0 DS1-y0 D, wherein C points are relative to D points closer to nanocomposite center, and the composition of C points and D points meets：x0 C ＜x0 D,y0 C＜y0 D.If quantum-dot structure unit is uniform alloy compositions structure（I.e. level width is consistent in the radial direction）, then its Alloy compositions are both preferably Cdx0Zn1-x0Sey0S1-y0, wherein, the alloy compositions of E points are Cdx0 EZn1-x0 ESey0 ES1-y0 E, F points Alloy compositions are Cdx0 FZn1-x0 FSey0 FS1-y0 F, wherein E points relative to F points closer to nanocomposite center, and E points and F The composition of point meets：x0 E=x0 F,y0 E=y0 F。
Specifically, there is alternate blue shift and constant during the reaction in the glow peak wavelength of the nanocomposite. There is blue shift and represent glow peak to the movement of shortwave direction, level width broadens, and red shift occurs and represents glow peak to the shifting of long wave direction Dynamic, level width narrows, and it is constant to represent level width if the constant representative of glow peak wavelength.Occur alternate blue shift and it is constant then It is alternately to change to represent level width, i.e., as shown in Fig. 2, in quantum dot in the radial direction, the level width in first interval It broadens（Blue shift）, level width is constant in second interval（It is constant）, level width broadens in 3rd interval（Blue shift）.
Specifically, as shown in Fig. 2, one kind is also prepared in the present invention there is inner alloy constituent to correspond to level width It is corresponded between level width and quantum-dot structure bosom and most external region containing at least no more than exterior alloy constituent The nanocomposite of the quantum-dot structure unit of one layer of uniform alloy compositions structure；That is, nanometer provided by the invention Composite material includes at least three quantum-dot structure units arranged successively in radial directions, wherein, at least three amount Son point structural unit in, the quantum-dot structure unit positioned at center and surface be in the radial direction more outside level width it is wider Graded alloy component structure, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions It is continuous, a quantum-dot structure unit between center and the quantum-dot structure unit on surface is uniform alloy compositions Structure.The structure of nanocomposite shown in Fig. 2 is known as concrete structure 2 in subsequent embodiment.
Specifically, in the nanocomposite provided such as Fig. 2, the quantum-dot structure unit positioned at center and surface it Between one layer of uniform alloy compositions structure quantum-dot structure unit on, the alloy compositions of any point are Cdx1Zn1-x1Sey1S1-y1, Wherein 0≤x1≤1,0≤y1≤1, and be 0 during x1 with y1 differences and be asynchronously 1, and x1 and y1 is fixed value.Such as certain The alloy compositions of any are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point also should be in the radial direction Cd0.5Zn0.5Se0.5S0.5；In another example in the quantum-dot structure unit of a certain uniform alloy compositions structure certain point homogeneous components For Cd0.7Zn0.3S, and the alloy compositions of another point also should be Cd in the quantum-dot structure unit0.7Zn0.3S；It is in another example a certain equal The homogeneous components of certain point are CdSe in the quantum-dot structure unit of one alloy compositions structure, and another in the quantum-dot structure unit The alloy compositions of any also should be CdSe.
Further, as in the nanocomposite of Fig. 2 offers, the quantum-dot structure unit positioned at center and surface is diameter The wider graded alloy component structure of more outside level width on direction, and graded alloy component adjacent in radial directions The energy level of the quantum-dot structure unit of structure is continuous；I.e. in the quantum-dot structure list with graded alloy component structure In member, radially the corresponding level width of alloy constituent of upper any point is greater than adjacent and closer to quantum The corresponding level width of alloy constituent of point structure centre another point.The quantum dot with graded alloy component structure Alloy compositions composition in structural unit is Cdx2Zn1-x2Sey2S1-y2, wherein 0≤x2≤1,0≤y2≤1, and x2 and y2 are not It is simultaneously 0 and be asynchronously 1.Such as the alloy compositions of certain point are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point are Cd0.3Zn0.7Se0.4S0.6。
Specifically, there is alternate blue shift and red shift during the reaction in the glow peak wavelength of the nanocomposite, To realize that the graded alloy component in specified location is distributed.There is blue shift and represent bands of a spectrum to the movement of shortwave direction, level width It broadens, red shift occurs and represent glow peak to the movement of long wave direction, level width narrows, and is represented if the constant representative of glow peak wavelength Level width is constant.It is alternately to change alternate blue shift and red shift occur then to represent level width, i.e., as shown in figure 3, measuring In the radial direction, level width broadens son point in first interval（Blue shift）, level width narrows in second interval（Red shift）, Level width broadens in 3rd interval（Blue shift）, level width narrows in the 4th section（Red shift）, the energy in the 5th section Level width broadens（Blue shift）.
Specifically, as shown in figure 3, a kind of full graded alloy component with quantum well structure is also prepared in the present invention Nanocomposite；That is, nanocomposite provided by the invention includes two kinds of quantum-dot structure unit（A1 Type and A2 types）, the wherein quantum-dot structure unit of A1 types is the wider gradual change of more outside level width in the radial direction Alloy compositions structure, the quantum-dot structure unit of A2 types is the narrower graded alloy group of more outside level width in the radial direction Separation structure, described two quantum-dot structure units are radially alternately distributed successively, and quantum adjacent in radial directions The energy level of point structural unit is continuous.That is, the quantum-dot structure cell distribution of the nanocomposite can be： A1, A2, A1, A2, A1 ... or A2, A1, A2, A1, A2 ..., that is, the quantum-dot structure unit originated can be A1 types, Can also be A2 types.In the quantum-dot structure unit of A1 types, level width is more more outside wider, in the amount of A2 types In son point structural unit, level width is more more outside narrower, both level structures are like the form of wave is radially Side upwardly extends, and the structure of nanocomposite shown in Fig. 3 is known as concrete structure 3 in subsequent embodiment.
Specifically, there is the blue shift being interrupted during the reaction in the glow peak wavelength of the nanocomposite.Occur blue Shifting represents glow peak and is moved to shortwave direction, and level width broadens.If certain glow peak wavelength occur red shift represent glow peak to Long wave direction is moved, and level width narrows, and it is constant to represent level width if the constant representative of glow peak wavelength.There is the indigo plant being interrupted It is mutation rather than consecutive variations to move the level width that then represents between quantum-dot structure unit, i.e., as shown in Figure 4.
Specifically, as shown in figure 4, a kind of alloy group of the quantum well structure with energy level mutation is also prepared in the present invention Point nanocomposite, specifically, the quantum-dot structure unit be in the radial direction more outside level width it is wider Graded alloy component structure, and the energy level of adjacent quantum-dot structure unit is discontinuous, i.e., each adjacent quantum dot knot The level width of structure unit has the characteristics that discontinuous variation, that is, is mutated feature, that is to say, that the alloy compositions of quantum dot are also With mutability, subsequent mutation structure principle is identical；The structure of nanocomposite shown in Fig. 4 is known as in subsequent embodiment Concrete structure 4.
Specifically, the nanocomposite described in Fig. 4, be by multiple quantum-dot structure units by way of mutation successively Arrangement is formed, these quantum-dot structure units are the graded alloy component knot that more outside level width is wider in the radial direction Structure.Further, in the nanocomposite, by paracentral quantum-dot structure unit level width be less than it is deep The level width of quantum-dot structure unit.That is, in the nanocomposite, from the level width of center to face It gradually broadens, so as to the funnel type structure that the opening for forming interruption becomes larger, certainly, the nanocomposite In, aforesaid way is also not limited to, i.e., the level width of deep quantum-dot structure unit might be less that close to center Quantum-dot structure unit level width, in this structure, the level width of adjacent quantum-dot structure unit, which has, staggeredly to be weighed Folded place.
Specifically, there is the red shift being interrupted during the reaction in the glow peak wavelength of the nanocomposite.Occur red Shifting represents glow peak and is moved to long wave direction, and level width narrows.If blue shift, which occurs, in glow peak wavelength represents glow peak to shortwave Direction is moved, and level width broadens, and it is constant to represent level width if the constant representative of glow peak wavelength.There is the red shift being interrupted then It is mutation rather than consecutive variations to represent the level width between quantum-dot structure unit, i.e., as shown in Figure 5.
Specifically, as shown in figure 5, the alloy of another quantum well structure with energy level mutation is also prepared in the present invention The nanocomposite of component, specifically, the quantum-dot structure unit be in the radial direction more outside level width it is narrower Graded alloy component structure, and the energy level of adjacent quantum-dot structure unit is discontinuous, i.e., each adjacent quantum dot The level width of structural unit has the characteristics that discontinuous variation, that is, is mutated feature, that is to say, that the alloy compositions of quantum dot It is with mutability, subsequent mutation structure principle is identical；The structure of nanocomposite shown in Fig. 5 is claimed in subsequent embodiment For concrete structure 5.
Specifically, the nanocomposite described in Fig. 5, be by multiple quantum-dot structure units by way of mutation successively Arrangement is formed, these quantum-dot structure units are the graded alloy component knot that more outside level width is narrower in the radial direction Structure.Further, in the nanocomposite, by paracentral quantum-dot structure unit level width be more than it is deep The level width of quantum-dot structure unit.That is, in the nanocomposite, from the level width of center to face It becomes narrow gradually, so as to form the gradually smaller funnel type structure of the opening of interruption, certainly, the nanocomposite In, aforesaid way is also not limited to, i.e., the level width of deep quantum-dot structure unit can also be more than close to center Quantum-dot structure unit level width, in this structure, the level width of adjacent quantum-dot structure unit, which has, staggeredly to be weighed Folded place.
Specifically, first there is blue shift during the reaction in the glow peak wavelength of the nanocomposite, then constant.Go out Existing blue shift represents glow peak and is moved to shortwave direction, and level width broadens, and it is wide to represent energy level if the constant representative of glow peak wavelength Spend it is constant, i.e., as shown in fig. 6, in quantum dot in the radial direction, level width broadens in first interval（Blue shift）, in the secondth area Interior level width is constant（It is constant）.
Specifically, as shown in fig. 6, a kind of nanocomposite is also prepared in the present invention, positioned at the nano combined material The level width of alloy constituent inside material is become larger, and quantum-dot structure most external region is equal by center to outside One alloy compositions；Specifically, the nanocomposite includes two amounts point structural unit（A3 types and A4 types）, In, the quantum-dot structure units of A3 types is the wider graded alloy component structure of more outside level width in the radial direction, A4 The quantum-dot structure unit of type is uniform alloy compositions structure, and the inside of the nanocomposite includes one or one The quantum-dot structure unit of a above graded alloy component structure, and graded alloy component structure adjacent in radial directions The energy level of quantum-dot structure unit be continuous；The outside of the nanocomposite includes one or more uniform The quantum-dot structure unit of alloy compositions structure；It is in subsequent embodiment that the structure of nanocomposite shown in Fig. 6 is referred to as specific Structure 6.
Specifically, in nanocomposite as shown in Figure 6, quantum-dot structure unit is distributed as A3 ... A3A4 ... A4, i.e., the inside of described nanocomposite are made of the quantum-dot structure unit of A3 types, the nanocomposite Outside is made of the quantum-dot structure unit of A4 types, and the amount of the quantity of the quantum-dot structure unit of A3 types and A4 types The quantity of son point structural unit is all higher than being equal to 1.
Further, there is continuous red shift during the reaction in the glow peak wavelength of the nanocomposite.Occur red Shifting represents glow peak and is moved to long wave direction, and level width narrows.If blue shift, which occurs, in glow peak wavelength represents glow peak to shortwave Direction is moved, and level width broadens, and it is constant to represent level width if the constant representative of glow peak wavelength.There is red shift representative to shine Peak is moved to long wave direction, and level width narrows, as shown in fig. 7, in quantum dot in the radial direction, the energy of quantum-dot structure unit Level width narrows（Red shift）.
Specifically, as shown in fig. 7, another nanocomposite is also prepared in the present invention, positioned at described nano combined The level width of the alloy constituent of material internal is uniform, the energy of the alloy constituent outside the quantum dot Level width is by center to outside to become larger；Specifically, the nanocomposite includes two amounts point structural unit（A5 Type and A6 types）, wherein, the quantum-dot structure units of A5 types is uniform alloy compositions structure, the quantum dot knot of A6 types Structure unit is the wider graded alloy component structure of more outside level width in the radial direction, the inside of the nanocomposite Include the quantum-dot structure unit of one or more uniform alloy compositions structure；The external of the nanocomposite is wrapped The quantum-dot structure unit of one or more graded alloy component structure is included, and gradual change adjacent in radial directions is closed The energy level of the quantum-dot structure unit of golden component structure is continuous；By nanocomposite shown in Fig. 7 in subsequent embodiment Structure is known as concrete structure 7.
Specifically, in nanocomposite as shown in Figure 7, monoatomic layer is distributed as A5 ... A5A6 ... A6, i.e. institute The inside for stating nanocomposite is made of the quantum-dot structure unit of A5 types, the outside of the nanocomposite be by The quantum-dot structure unit composition of A6 types, and the quantum-dot structure of the quantity of the quantum-dot structure unit of A5 types and A6 types The quantity of unit is all higher than being equal to 1.
Further, quantum-dot structure unit provided by the present invention includes 2-20 layers of monoatomic layer.Preferably, the amount Son point structural unit includes 2-5 monoatomic layer, and the preferred number of plies can ensure that quantum dot realizes good photoluminescence quantum yield And efficient charge injection efficiency.
Further, the quantum dot light emitting unit includes 1-10 layer crystals born of the same parents layer, preferably 2-5 layer crystals born of the same parents layer；The structure cell layer For minimum structural unit, i.e., its alloy compositions of each layer of structure cell layer are fixed, i.e., have the phase isomorphous in each structure cell layer Lattice parameter and element, the closed unit cell curved surface that each quantum-dot structure unit is the connection of structure cell layer and forms, adjacent cell layer Between level width have continuous structure or mutation structure.
The cation presoma includes：The presoma of Zn, the presoma of the Zn is zinc methide（dimethyl Zinc）, diethyl zinc（diethyl Zinc）, zinc acetate（Zinc acetate）, zinc acetylacetonate（Zinc acetylacetonate）, zinc iodide（Zinc iodide）, zinc bromide（Zinc bromide）, zinc chloride（Zinc chloride）, zinc fluoride（Zinc fluoride）, zinc carbonate（Zinc carbonate）, zinc cyanide（Zinc cyanide）、 Zinc nitrate（Zinc nitrate）, zinc oxide（Zinc oxide）, zinc peroxide（Zinc peroxide）, zinc perchlorate（Zinc perchlorate）, zinc sulfate（Zinc sulfate）, zinc oleate（Zinc oleate）Or zinc stearate（Zinc stearate）At least one of Deng, but not limited to this.
The cation presoma includes the presoma of Cd, and the presoma of the Cd is dimethyl cadmium（dimethyl cadmium）, diethyl cadmium（diethyl cadmium）, cadmium acetate（cadmium acetate）, acetylacetone,2,4-pentanedione cadmium（cadmium acetylacetonate）, cadmium iodide（cadmium iodide）, cadmium bromide（cadmium bromide）, caddy （cadmium chloride）, cadmium fluoride（cadmium fluoride）, cadmium carbonate（cadmium carbonate）, cadmium nitrate （cadmium nitrate）, cadmium oxide（cadmium oxide）, cadmium perchlorate（cadmium perchlorate）, cadmium phosphate （cadmium phosphide）, cadmium sulfate（cadmium sulfate）, cadmium oleate（cadmium oleate）Or cadmium stearate （cadmium stearate）At least one of Deng, but not limited to this.
The anion presoma includes the presoma of Se, such as Se arbitrarily combines formed chemical combination with some organic matters Object can be specifically Se-TOP (selenium-trioctylphosphine), Se-TBP (selenium- tributylphosphine)、Se-TPP (selenium-triphenylphosphine)、Se-ODE (selenium-1- octadecene)、Se-OA (selenium-oleic acid)、Se-ODA (selenium-octadecylamine)、Se- TOA (selenium-trioctylamine), Se-ODPA (selenium-octadecylphosphonic acid) or Se- At least one of OLA (selenium-oleylamine) etc., but not limited to this.
The anion presoma includes the presoma of S, such as S arbitrarily combines formed chemical combination with some organic matters Object can be specifically S-TOP (sulfur-trioctylphosphine), S-TBP (sulfur-tributylphosphine) 、S-TPP(sulfur-triphenylphosphine)、S-ODE (sulfur-1-octadecene) 、S-OA (sulfur- oleic acid)、S-ODA(sulfur-octadecylamine)、S-TOA(sulfur-trioctylamine) 、S-ODPA At least one of (sulfur-octadecylphosphonic acid) or S-OLA (sulfur-oleylamine) etc., but It is without being limited thereto；The presoma of the S can also be alkyl hydrosulfide (alkyl thiol), and the alkyl hydrosulfide can be hexyl mercaptan (hexanethiol), spicy thioalcohol (octanethiol), decyl mercaptan (decanethiol), lauryl mercaptan (dodecanethiol), hexadecyl mercaptan (hexadecanethiol) or mercapto propyl silanes At least one of (mercaptopropylsilane) etc., but not limited to this.
The anion presoma includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP, Te-TPP, At least one of Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA etc..
Above-mentioned cation precursor and anion presoma can form to determine choosing according to final nanocomposite Select one or more therein：Such as it needs to synthesize CdxZn1-xSeyS1-yNanocomposite when, then need Cd presoma, The presoma of Zn, the presoma of Se, S presoma；If desired for synthesis CdxZn1-xDuring the nanocomposite of S, then need Cd's Presoma, the presoma of Zn, S presoma；If desired for synthesis CdxZn1-xDuring the nanocomposite of Se, then before needing Cd Drive the presoma of body, the presoma of Zn, Se.
In the preparation process in accordance with the present invention, the condition that cation exchange reaction occurs preferably carries out heating reaction, such as Heating temperature is between 100 DEG C to 400 DEG C, between preferred heating temperature is 150 DEG C to 380 DEG C.Heating time is in 2s to for 24 hours Between, preferred heating time is 5min between 4h.
Heating temperature is higher, and the rate of cation exchange reaction is faster, the thickness range of cation exchange and exchange degree Also it is bigger, but thickness and extent and scope can progressively reach the degree of relative saturation；Similar, heating time is longer, and cation is handed over The thickness range and exchange degree changed is also bigger, but thickness and extent and scope can also progressively reach the degree of relative saturation.Sun from The thickness range and degree that son exchanges directly determine formed graded alloy component distribution.Cation exchange is formed gradually Become alloy compositions distribution also to be determined by the binary or the thickness of multi-element compounds nanocrystal that are respectively formed simultaneously.
When forming each layer compound, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:50（Tool Molar feed ratio of the body for cation and anion）, such as when forming first layer compound, cationic presoma and anion The molar ratio of presoma is 100:1 to 1:50；When forming second layer compound, cationic presoma and anion presoma Molar ratio is 100:1 to 1:50, preferred ratio is 20:1 to 1:10, preferred cation presoma and anion presoma Molar ratio can ensure reaction rate in easily controllable range.
The present invention also provides a kind of nanocomposite, wherein, the nanocomposite is prepared using as described above Method is prepared.
By the nanocomposite prepared by above-mentioned preparation method, glow peak wave-length coverage is received for 400 nanometers to 700 Rice, preferred glow peak wave-length coverage are 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can ensure Quantum dot realizes the photoluminescence quantum yield more than 30% within this range.
By the nanocomposite prepared by above-mentioned preparation method, photoluminescence quantum yield ranging from 1% to 100%, preferably Photoluminescence quantum yield ranging from 30% to 100%, can ensure well should for quantum dot in the range of preferred photoluminescence quantum yield The property used.
Further, in the present invention, the peak width at half height of the glow peak of the nanocomposite is 12 nanometers to 80 nanometers.
The present invention also provides a kind of semiconductor devices, including nanocomposite as described above.
The semiconductor devices is electroluminescent device, photo luminescent devices, solar cell, display device, photoelectricity are visited Survey any one in device, bioprobe and device for non-linear optical.
By taking electroluminescent device as an example, using nanocomposite of the present invention as the quantum dot of emitting layer material electricity Electroluminescence device QLED.This quanta point electroluminescent device can be realized：1) high efficiency charge injection, 2) high brightness, 3) low driving voltage, 4) the excellent devices performance such as high device efficiency.Meanwhile nanocomposite of the present invention, have The characteristics of easily controllable and diversity level structure, can fully meet the level structure of other functional layers in simultaneously coordination device, To realize the matching of device entirety level structure, so as to help to realize the QLED devices of efficient stable.
The photo luminescent devices refer to that relying on external light source is irradiated, and so as to obtain energy, generating excitation causes to send out The device of light, ultraviolet radioactive, visible ray and infra-red radiation can cause luminescence generated by light, such as phosphorescence and fluorescence.The present invention's receives Meter Jing Ti can be as the luminescent material of photo luminescent devices.
The solar cell is also referred to as photovoltaic device, and nanocrystal of the invention can be as the light absorption material of solar cell Material effectively improves the properties of photovoltaic device.
The display device refers to the display panel of backlight module or the application backlight module, and the display panel can be with It applies in various products, such as display, tablet computer, mobile phone, laptop, flat panel TV, wearable display Equipment or other include the products of different size display panels.
The photodetector refers to optical signal can be converted to the device of electric signal, and principle is to be caused to be shone by radiation It penetrates material electric conductivity to change, quanta point material is applied in photodetector, there is following advantage：To vertical incidence light Sensitive, photoconductive response degree height, specific detecivity are high, detection wavelength is continuously adjusted and can low temperature preparation.The photoelectricity of this structure is visited Survey device in the process of running, quantum dot light photosensitive layer（Nanocrystal i.e. using the present invention）Absorb the photoproduction electricity generated after photon To can be detached under the action of built in field, this causes the structure photodetector to have lower driving in son-hole Voltage can just work, and easily controllable under low applying bias even 0 applying bias.
The bioprobe refers to modify certain class material, makes it have the device of mark function, such as to this hair Bright nanocrystal is coated, and so as to form fluorescence probe, is applied in cell imaging or substance detection field, relative to Traditional organic fluorescent dye probe, bioprobe prepared by nanocrystal using the present invention have fluorescence intensity height, chemistry The characteristics of stability is good, anti-light bleaching power is strong, tool has been widely used.
The device for non-linear optical belongs to optical lasers technical field, using wide, such as opens the light for electric light And Laser Modulation, the tuning of conversion, laser frequency for laser frequency；Carry out optical Information Processing, improve image quality and Beam quality；As nonlinear etalon and bistable device；The highly excited level and high-resolution spectroscopy and object of research substance Transfer process and other relaxation processes of matter internal energy and excitation etc..
Embodiment 1：Preparation based on CdZnSeS/CdZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn, the presoma of anion Se and anion S are noted Enter into reaction system, form CdyZn1-ySebS1-bLayer（Wherein 0≤y≤1,0≤b≤1）；Continue the forerunner of cationic Cd Body, the presoma of cation Zn, the presoma of anion Se and the presoma of anion S are injected into reaction system, above-mentioned CdyZn1-ySebS1-bLayer surface forms CdzZn1-zSecS1-cLayer（Wherein 0≤z≤1, and z is not equal to y, 0≤c≤1）；Certain Heating temperature and the reaction conditions such as heating time under, ectonexine nanocrystal occurs（I.e. above-mentioned two layers of compound）Middle Cd and Zn The exchange of ion；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller, It can be in CdyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cThe near interface of layer forms the graded alloy component of Cd contents and Zn contents Distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1,0≤a≤1.
Embodiment 2：Preparation based on CdZnS/CdZnS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion S is injected into reaction system, It is initially formed CdyZn1-yS layers（Wherein 0≤y≤1）；Continue by the presoma of cationic Cd, cation Zn presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can be in above-mentioned CdyZn1-yS layer surfaces form CdzZn1-zS layers（Wherein 0≤z≤1, And z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, ectonexine nanocrystal occurs（It is i.e. above-mentioned Two layers of compound）The exchange of middle Cd and Zn ions；Since the limited and more remote migration distance of the migration distance of cation is moved The probability of shifting, therefore can be in Cd with regard to smalleryZn1-yS layers and CdzZn1-zS layers of near interface forms Cd contents and Zn contents gradually Become alloy compositions distribution, i.e. CdxZn1-xS, wherein 0≤x≤1.
Embodiment 3：Preparation based on CdZnSe/CdZnSe quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion Se is injected into reaction system It is initially formed CdyZn1-ySe layers（Wherein 0≤y≤1）；Continue the presoma and the moon of the presoma of cationic Cd, cation Zn The presoma of ion Se is injected into reaction system, can be in above-mentioned CdyZn1-ySe layer surfaces form CdzZn1-zSe layers（Wherein 0≤z ≤ 1, and z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, Cd in ectonexine nanocrystal occurs With the exchange of Zn ions；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller, It therefore can be in CdyZn1-ySe layers and CdzZn1-zSe layers of near interface forms the graded alloy component point of Cd contents and Zn contents Cloth, i.e. CdxZn1-xSe, wherein 0≤x≤1.
Embodiment 4：Preparation based on CdS/ZnS quantum dots
First the presoma of the presoma of cationic Cd and anion S is injected into reaction system, is initially formed CdS layer；Continuing will The presoma of cationic Zn and the presoma of anion S are injected into reaction system, can form ZnS layers on above-mentioned CdS layer surface； Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that migrates of the limited and more remote migration distance of migration distance with regard to smaller, therefore can be in CdS layer and ZnS layers of interface Be formed about Cd contents it is radially outward gradually decrease, the radially outward graded alloy component gradually increased point of Zn contents Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 5：Preparation based on CdSe/ZnSe quantum dots
First the presoma of the presoma of cationic Cd and anion Se is injected into reaction system and is initially formed CdSe layers；Continuing will The presoma of cationic Zn and the presoma of anion Se are injected into reaction system, can form ZnSe in above-mentioned CdSe layer surfaces Layer；Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Cd cations, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in CdSe layers and ZnSe layer with regard to smaller Near interface formed Cd contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Zn contents Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 6：Preparation based on CdSeS/ZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of anion Se and anion S is injected into reaction system It is initially formed CdSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Zn, anion Se presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can be in above-mentioned CdSebS1-bLayer surface forms ZnSecS1-cLayer（Wherein 0≤c≤1）； Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that migrates of the limited and more remote migration distance of migration distance with regard to smaller, therefore can be in CdSebS1-bLayer with ZnSecS1-cThe near interface of layer formed Cd contents it is radially outward gradually decrease, Zn contents are radially outward gradually increases Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x is from inside to outside（Radial direction）From 1 monotone decreasing It is 0,0≤a≤1.
Embodiment 7：Preparation based on ZnS/CdS quantum dots
First the presoma of the presoma of cationic Zn and anion S is injected into reaction system and is initially formed ZnS layers；Continuing will be positive The presoma of ion Cd and the presoma of anion S are injected into reaction system, can form CdS layer in above-mentioned ZnS layer surfaces； Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Zn sun Cation exchange reaction occurs for ion, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that the limited and more remote migration distance of migration distance migrates, therefore can be attached with the interface of CdS layer at ZnS layers with regard to smaller It is near formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy component point gradually increased of Cd contents Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 8：Preparation based on ZnSe/CdSe quantum dots
First the presoma of the presoma of cationic Zn and anion Se is injected into reaction system and is initially formed ZnSe layer；Continuing will The presoma of cationic Cd and the presoma of anion Se are injected into reaction system, can form CdSe on above-mentioned ZnSe layer surface Layer；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in ZnSe layer and CdSe layers with regard to smaller Near interface formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Cd contents Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 9：Preparation based on ZnSeS/CdSeS quantum dots
First the presoma of the presoma of cationic Zn, the presoma of anion Se and anion S is injected into reaction system It is initially formed ZnSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Cd, anion Se presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can form CdSe in above-mentioned ZnSebS1-b layer surfacescS1-cLayer（Wherein 0≤c≤ 1）；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in ZnSe with regard to smallerbS1-bLayer with CdSecS1-cThe near interface of layer formed Zn contents it is radially outward gradually decrease, Cd contents are radially outward gradually increases Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x are from inside to outside 1 from 0 monotonic increase, 0≤a≤ 1。
Embodiment 10：Blue quantum dot Cd with concrete structure 1xZn1-xThe preparation of S
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, CdxZn1-xS is nucleated rapidly, after reacting 10 min, by the trioctylphosphine sulfide presoma and 6 mL of 3 mL Cadmium oleate presoma is injected into reaction system simultaneously with the rate of 3 mL/h and 10 mL/h respectively.After reaction, it waits to react After liquid is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, is then centrifuged for purifying, obtain that there is opening The blue quantum dot Cd of the funnel type level structure become largerxZn1-xS, as shown in figure 8, its glow peak wavelength is 453nm, Absorbance is continuously decreased with the increase of wavelength.
Embodiment 11：Green quantum dot Cd with concrete structure 1xZn1-xSeyS1-y /CdzZn1-zThe preparation of S
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4 mL Octyl group phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, CdxZn1-xSeyS1-yRapid nucleation, after reacting 10 min, by the sulphur of 2 mL Change tri octyl phosphine presoma to be added dropwise in reaction system with the rate of 8 mL/h, until presoma has injected.Reaction terminates Afterwards, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification is had Be open the green quantum dot Cd of funnel type level structure become largerxZn1-xSeyS1-y /CdzZn1-zS；As shown in figure 9, it is sent out Peak wavelength is 542nm, and absorbance is continuously decreased with the increase of wavelength.
Embodiment 12：Red quantum dot Cd with concrete structure 1xZn1-xSeyS1-y/CdzZn1-zThe preparation of S
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet) 2], 14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then will It is switched under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, CdxZn1-xSe is nucleated rapidly, after reacting 10 min, by selenizing tri octyl phosphine-vulcanization of 2 mL Tri octyl phosphine presoma is added dropwise to the rate of 4 mL/h in reaction system.After reaction, treat that reaction solution is cooled to room Product with toluene and absolute methanol is dissolved, precipitated by Wen Hou repeatedly, and centrifugation purification obtains the funnel become larger with opening The Cd of type level structurexZn1-xSeyS1-y/CdzZn1-zS red fluorescence quantum dots；As shown in Figure 10, glow peak wavelength is 631nm, absorbance are continuously decreased with the increase of wavelength..
Embodiment 13：The influence that cadmium oleate charge velocity synthesizes the blue quantum dot with concrete structure 1
On the basis of embodiment 10, by adjusting the charge velocity of cadmium oleate, the gradient that can regulate and control the ingredient of quantum dot becomes The slope of change, so as to influence the variation of its infundibulate level structure, the final regulation and control realized to quantum dot light emitting wavelength.
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet) 2], 8 mL oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, CdxZn1-xS is nucleated rapidly, after reacting 10 min, by the trioctylphosphine sulfide presoma of 3 mL with 3 ML/h rates are added dropwise in reaction system, while cadmium oleate presoma is added dropwise to reaction with different charge velocities In system.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, from The heart purifies, and obtains the blue-fluorescence Cd of funnel type level structure become larger with openingxZn1-xS/CdyZn1-yS quantum dots.
Based on identical core（Alloy quantum dot glow peak 447nm）And alloy under the charge velocity of different cadmium oleate presomas Quantum dot light emitting wavelength, the charge velocity for adjusting cadmium oleate presoma realize being listed as follows for quantum dot light emitting wavelength tuning control：
Cadmium oleate charge velocity（mmol/h） Emission wavelength（nm）
0.5 449
0.75 451
1 453
1.25 455
1.5 456
Embodiment 14：The influence that cadmium oleate injection rate synthesizes the blue quantum dot with concrete structure 1
On the basis of embodiment 10 and embodiment 13, by adjusting the injection rate of cadmium oleate, the ingredient of quantum dot can be regulated and controled Graded section, so as to influence the variation of its infundibulate level structure, the final tune realized to quantum dot light emitting wavelength Control.Based on identical core（Alloy quantum dot glow peak 447nm）And the injection rate of different cadmium oleate presomas（Identical charge velocity Lower 1 mmol/h）Alloy quantum dot emission wavelength under rate, such as following table：
Cadmium oleate injection rate（mmol） Emission wavelength（nm）
0.4 449
0.5 451
0.6 453
0.8 454
1.0 455
Embodiment 15：The preparation of blue quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）With 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, then by 2mL by S Trioctylphosphine sulfide presoma and 6mL cadmium oleates presoma reaction is injected into the rate of 3 mL/h and 10mL/h simultaneously respectively In system.After injecting 40 min, temperature of reaction system is warming up to 310 DEG C, by 1mL trioctylphosphine sulfides presoma with 3 mL/h Rate be injected into reaction system, after reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot of Quantum Well.
Embodiment 16：The preparation of green quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet) 2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL Octyl group phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system temperature Degree is down to 280 DEG C, then by the trioctylphosphine sulfide presoma of 1.2mL and 6mL cadmium oleates presoma respectively with 2 mL/h and The rate of 10mL/h is injected into reaction system, until presoma has injected.Temperature of reaction system is warming up to 310 DEG C, by 0.8 ML trioctylphosphine sulfides presoma is injected into the rate of 2 mL/h in reaction system.After reaction, treat that reaction solution is cooled to After room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having Quantum Well Green quantum dot.
Embodiment 17：The preparation of red quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.3 mmol cadmium oxides（CdO）, 0.3mL oleic acid（Oleic acid）With 2.7 mL octadecylenes（1- Octadecene）It is placed in 50 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, then by Se By 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide presoma and 3mL cadmium oleates presoma respectively with the speed of 2 mL/h and 6 mL/h Rate is injected into reaction system.Temperature of reaction system is warming up to 310 DEG C, before 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide Body is driven to be injected into reaction system with the rate of 4 mL/h.After reaction, after reaction solution is cooled to room temperature, with toluene and nothing Product is dissolved, precipitated by water methanol repeatedly, and centrifugation purification obtains the red quantum dot with Quantum Well.
Embodiment 18：The preparation of blue quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.2 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS is nucleated rapidly, after reacting 10 min, by cadmium oleate presoma and vulcanization trioctylphosphine Phosphine presoma is continuously injected into the rate of 0.6 mmol/h, 4 mmol/h in 20 min to reaction system respectively.Then by oleic acid Cadmium presoma, trioctylphosphine sulfide presoma and selenizing tri octyl phosphine presoma respectively with 0.4 mmol/h, 0.6 mmol/h and The rate of 0.2 mmol/h is continuously injected into 1 h to reaction system.After reaction, after reaction solution is cooled to room temperature, first is used Product is dissolved, precipitated by benzene and absolute methanol repeatedly, and centrifugation purification obtains the blue quantum dot with Quantum Well (CdZnS/CdZnS/CdZnSeS3)。
Embodiment 19：The preparation of green quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4 mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 0.1 mmol selenium powders（Selenium powder）, 0.3 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 0.8 mmol sulphur powders（Sulfur powder）, 0.8 mmol selenium powders（Selenium powder）It is dissolved in 3 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 3.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma 1 is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 5 min, by the selenizing of 2mL Tri octyl phosphine-trioctylphosphine sulfide presoma 2 is added dropwise to the rate of 6 mL/h in reaction system.Then, by the selenium of 3mL Change the cadmium oleate presoma of tri octyl phosphine-trioctylphosphine sulfide presoma 3 and 6mL respectively with 3 mL/h and 6 mL/h rates after It is continuous to be added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the green quantum dot (CdZn with Quantum Well3SeS3/Zn4SeS3/ Cd3Zn5Se4S4)。
Embodiment 20：The preparation of red quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.9 mmol cadmium oxides（CdO）, 0.9 mL oleic acid（Oleic acid）With 8.1 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xSe, it is after reacting 10 min, selenizing tri octyl phosphine-vulcanization three of 2 mL is pungent Base phosphine presoma is added dropwise to the rate of 2 mL/h in reaction system.When being injected into 30 min, before the cadmium oleate of 3 mL Body is driven to be added dropwise in reaction system with 6 mL/h rates simultaneously.After reaction, after reaction solution is cooled to room temperature, first is used Product is dissolved, precipitated by benzene and absolute methanol repeatedly, and centrifugation purification obtains the red quantum dot with Quantum Well （CdxZn1-xSe/ZnSeyS1-y/CdzZn1-zSeS）.
Embodiment 21：The preparation of blue quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.2mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1mL（Trioctylphosphine） In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine presoma It is continuously injected into 20 min to reaction system with the rate of 0.6 mmol/h, 0.6 mmol/h respectively.Then by cadmium oleate forerunner Body and trioctylphosphine sulfide presoma are continuously injected into the rate of 0.4 mmol/h and 6 mmol/h in 1h to reaction system respectively. After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification, Obtain the blue quantum dot with Quantum Well（CdZnS/CdZnSe/CdZnS）.
Embodiment 22：The preparation of green quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.4 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 2 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.8 mmol cadmium oxides（CdO）, 1.2 mL oleic acid（Oleic acid）With 4.8 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine presoma It is continuously injected into 40 min to reaction system with the rate of 0.6 mmol/h, 0.6 mmol/h respectively.Then by cadmium oleate forerunner Body and trioctylphosphine sulfide presoma are continuously injected into 1 h to reaction system with the rate of 0.4 mmol/h and 6 mmol/h respectively In.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation carries It is pure, obtain the green quantum dot with Quantum Well（CdZnS/CdZnSe/CdZnS）.
Embodiment 23：The preparation of red quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1.5 mmol selenium powders（Selenium powder）, 1.75 mmol sulphur powders（Sulfur powder）It is dissolved in 3mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 1 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.8 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 3 mmol cadmium oxides（CdO）, 3mL oleic acid（Oleic acid）With 6 mL octadecylenes（1-Octadecene）It is placed in In 100 mL three-necked flasks, it is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent cadmium oleate presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma 1 is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by the selenizing trioctylphosphine of 2 mL The cadmium oleate presoma of phosphine presoma and 3mL are added dropwise to the rate of 4 mL/h and 6 mL/h in reaction system respectively.Note When entering to 30 min, by the cadmium oleate presoma of selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2 of 2mL and 3mL respectively with 2 mL/h and 3 mL/h rates are added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, toluene is used Product is dissolved repeatedly with absolute methanol, is precipitated, centrifugation purification obtains the red quantum dot of Quantum Well（CdxZn1- xSe/CdZnSe/CdzZn1-zSeS）.
Embodiment 24：The preparation of blue quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by 3 mL trioctylphosphine sulfides presomas with 3 mL/h's Rate is continuously injected into 1h to reaction system, when trioctylphosphine sulfide presoma injects 20 min, by 2 mL cadmium oleate forerunners Body is injected into 6 mL/h in reaction system, when trioctylphosphine sulfide presoma injects 40 min, by 4 mL cadmium oleate forerunners Body is injected into 12 mL/h in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol Product is dissolved repeatedly, is precipitated, centrifugation purification obtains the blue quantum dot with Quantum Well（CdZnS/ZnS/ CdZnS）.
Embodiment 25：The preparation of green quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, 3 mL are vulcanized three Octyl group phosphine presoma is continuously injected into the rate of 3 mL/h in 1h to reaction system, injects 20 in trioctylphosphine sulfide presoma During min, 2 mL cadmium oleates presomas are injected into 6 mL/h in reaction system, inject 40 in trioctylphosphine sulfide presoma During min, 4 mL cadmium oleates presomas are injected into 12 mL/h in reaction system.After reaction, treat that reaction solution is cooled to room Product with toluene and absolute methanol is dissolved, precipitated by Wen Hou repeatedly, and centrifugation purification obtains having the green of Quantum Well Color quantum dot（CdZnSeS/ZnS/CdZnS）.
Embodiment 26：The preparation of red quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by trioctylphosphine sulfide presoma with 6 mmol/ The rate of h is continuously injected into 1h to reaction system, when S-TOP injects 20 min, by 0.2 mmol cadmium oleate presomas with 0.6 Mmol/h is injected into reaction system, when S-TOP injects 40 min, by 0.4 mmol cadmium oleates presoma with 1.2 mmol/h It is injected into reaction system.After reaction, it is with toluene and absolute methanol that product is repeatedly molten after reaction solution is cooled to room temperature Solution, precipitation, centrifugation purification, obtain the red quantum dot with Quantum Well（CdZnSe/ZnS/CdZnS）.
Embodiment 27：The preparation of blue quantum dot with concrete structure 6
It is prepared by sour cadmium and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL oil Acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C true 60 min of sky degassing.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by trioctylphosphine sulfide presoma and cadmium oleate presoma It is added dropwise in reaction system with the rate of 6mmol/h and 0.6 mmol/h respectively.After 30 min, temperature of reaction system is dropped To 280 DEG C, by remaining trioctylphosphine sulfide presoma and cadmium oleate presoma respectively with the speed of 6mmol/h and 0.6 mmol/h Rate is added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot with concrete structure 6（CdxZn1-xS）.
Embodiment 28：The preparation of green quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL Octyl group phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system temperature Degree is down to 280 DEG C, and trioctylphosphine sulfide presoma is added dropwise to the rate of 4 mL/h in reaction system.Reaction terminates Afterwards, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification is had The green quantum dot of concrete structure 6（CdxZn1-xSeyS1-y/ZnS）.
Embodiment 29：The preparation of red quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then by it It switches under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, CdxZn1-xSe is nucleated rapidly, and after reacting 10 min, temperature of reaction system is down to 280 DEG C, will Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma is added dropwise to the rate of 4 mL/h in reaction system.After reaction, After reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having tool The red quantum dot of body structure 6（CdxZn1-xSe/ZnSeS）.
Embodiment 30：The preparation of blue quantum dot with concrete structure 7
It is prepared by the first presoma of cadmium oleate：By 1 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then it switches it to Into under nitrogen atmosphere, and in preservation at this temperature in case for use.
It is prepared by the second presoma of cadmium oleate：By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 for 250 DEG C under nitrogen atmosphere Mins obtains transparent the second presoma of cadmium oleate.
It is prepared by oleic acid zinc precursor：By 9 mmol zinc acetates [Zn (acet) 2], 7 mL oleic acid（Oleic acid）And 10 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then It switches it under nitrogen atmosphere, and is heated to reflux preserving in case for use in lower 250 DEG C of nitrogen atmosphere.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, the first presoma of cadmium oleate is warming up to 310 DEG C, sulphur octadecylene presoma is rapidly injected Into reaction system, CdS is quickly generated, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, then by 3 The trioctylphosphine sulfide presoma of mL and 6 the second presomas of mL cadmium oleates are noted simultaneously with the rate of 3 mL/h and 10 mL/h respectively Enter into reaction system.
After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, Centrifugation purification, obtains the blue quantum dot with Quantum Well.
Embodiment 31：The preparation of green quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.4 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, it is dissolved in the tri octyl phosphine of 4 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine.
It is prepared by oleic acid zinc precursor：By 8 mmol zinc acetates [Zn (acet)2], 9 mL oleic acid（Oleic acid）With 15 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.In nitrogen Atmosphere encloses lower 250 DEG C and is heated to reflux 120 mins, obtains transparent oleic acid zinc precursor.
By 2 mmol sulphur powders（Sulfur powder）With 1.6 mmol selenium powders（Selenium powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected Into reaction system, CdSe is quickly generated, after reacting 5 mins, oleic acid zinc precursor is all injected into reaction system, by 2 Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of mL is added dropwise to the rate of 2 mL/h in reaction system, until before Body is driven to have injected.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is sunk It forms sediment, centrifugation purification obtains the green fluorescence quantum dot with Quantum Well.
Embodiment 32：The preparation of red quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.8 mmol cadmium oxides（CdO）, 4 mL oleic acid（Oleic acid）With 10 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
It is prepared by oleic acid zinc precursor：12 mmol zinc acetates [Zn (acet)2], 10 mL oleic acid（Oleic acid）With 10 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.
By 0.8 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, Obtain selenizing tri octyl phosphine presoma.
By 1 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected Into reaction system, CdSe is quickly generated, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, it will Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of 2 mL is added dropwise to the rate of 4 mL/h in reaction system.Reaction After, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains Red fluorescence quantum dot with Quantum Well.
Embodiment 33
The present embodiment light emitting diode with quantum dots as shown in figure 11, includes successively from bottom to top：ITO substrates 11, hearth electrode 12, PEDOT：PSS hole injection layers 13, poly-TPD hole transmission layers 14, quantum dot light emitting layer 15, ZnO electron transfer layers 16 and Al Top electrode 17.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 12,30 nm PEDOT are sequentially prepared on ITO substrates 11：13 and 30 nm poly-TPD of PSS hole injection layers After hole transmission layer 14, one layer of quantum dot light emitting layer 15 is prepared on poly-TPD hole transmission layers 14, thickness is 20 nm, with Prepare 40 nm ZnO electron transfer layers 16 and 100 nm Al top electrodes 17 on quantum dot light emitting layer 15 again afterwards.The quantum dot The nanocomposite of luminescent layer 15 is nanocomposite as described in Example 10.
Embodiment 34
Light emitting diode with quantum dots in the present embodiment as shown in figure 12, includes successively from bottom to top：ITO substrates 21, hearth electrode 22、PEDOT：PSS hole injection layers 23, Poly (9-vinylcarbazole) (PVK) hole transmission layer 24, quantum dot light emitting Layer 25, ZnO electron transfer layers 26 and Al top electrodes 27.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 22,30 nm PEDOT are sequentially prepared on ITO substrates 21：23 and 30 nm PVK holes of PSS hole injection layers After transport layer 24, one layer of quantum dot light emitting layer 25 is prepared on PVK hole transmission layers 24, thickness is 20 nm, then again in quantum 40 nm ZnO electron transfer layers 26 and 100 nm Al top electrodes 27 are prepared on point luminescent layer 25.The quantum dot light emitting layer 25 Nanocomposite is nanocomposite as described in Example 15.
Embodiment 35
The present embodiment light emitting diode with quantum dots as shown in figure 13, includes successively from bottom to top：ITO substrates 31, hearth electrode 32, PEDOT：PSS hole injection layers 33, poly-TPD hole transmission layers 34, quantum dot light emitting layer 35, TPBi electron transfer layers 36 and Al top electrodes 37.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 32,30 nm PEDOT are sequentially prepared on ITO substrates 31：33 and 30 nm poly-TPD of PSS hole injection layers After hole transmission layer 34, one layer of quantum dot light emitting layer 35 is prepared on poly-TPD hole transmission layers 34, thickness is 20 nm, with 30 nm TPBi electron transfer layers 36 are prepared by vacuum deposition method on quantum dot light emitting layer 35 again afterwards and 100 nm Al are pushed up Electrode 37.The nanocomposite of the quantum dot light emitting layer 35 is nanocomposite as described in Example 18.
Embodiment 36
The present embodiment light emitting diode with quantum dots as shown in figure 14, includes successively from bottom to top：ITO substrates 41, hearth electrode 42, ZnO electron transfer layers 43, quantum dot light emitting layer 44, NPB hole transmission layers 45, MoO3Hole injection layer 46 and Al top electrodes 47.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
42,40 nm ZnO electron transfer layers 43 of hearth electrode are sequentially prepared on ITO substrates 41, on ZnO electron transfer layers 43 One layer of quantum dot light emitting layer 44 is prepared, thickness is 20 nm, then prepares 30 nm NPB holes by vacuum deposition method again 45,5 nm MoO of transport layer346 and 100 nm Al top electrodes 47 of hole injection layer.The nanometer of the quantum dot light emitting layer 44 is answered Condensation material is nanocomposite as described in Example 21.
Embodiment 37
The present embodiment light emitting diode with quantum dots as shown in figure 15, includes successively from bottom to top：Glass substrate 51, Al electrodes 52, PEDOT：PSS hole injection layers 53, poly-TPD hole transmission layers 54, quantum dot light emitting layer 55, ZnO electron transfer layers 56 and ITO top electrodes 57.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
100 nm Al electrodes 52 are prepared by vacuum deposition method in glass substrate 51, are then sequentially prepared 30 nm PEDOT：After 53 and 30 nm poly-TPD hole transmission layers 54 of PSS hole injection layers, on poly-TPD hole transmission layers 54 One layer of quantum dot light emitting layer 55 is prepared, thickness is 20 nm, then prepares 40 nm ZnO electronics on quantum dot light emitting layer 55 again Transport layer 56 prepares 120 nm ITO as top electrode 57 finally by sputtering method.The nanometer of the quantum dot light emitting layer 55 Composite material is nanocomposite as described in Example 24.
Embodiment 38
The present embodiment light emitting diode with quantum dots as shown in figure 16, includes successively from bottom to top：Glass substrate 61, Al electrodes 62, ZnO electron transfer layers 63, quantum dot light emitting layer 64, NPB hole transmission layers 65, MoO3Hole injection layer 66 and ITO top electrodes 67.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
100 nm Al electrodes 62 are prepared by vacuum deposition method in glass substrate 61, are then sequentially prepared 40 nm ZnO 63,20 nm quantum dot light emitting layers 64 of electron transfer layer then prepare 30 nm NPB hole transports by vacuum deposition method again 65,5 nm MoO of layer3Hole injection layer 66 prepares 120 nm ITO as top electrode 67 finally by sputtering method.The amount The nanocomposite of son point luminescent layer is nanocomposite as described in Example 27.
It should be understood that the application of the present invention is not limited to the above, it for those of ordinary skills, can To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect range.

Claims (22)

1. a kind of preparation method of nanocomposite, which is characterized in that including step：
Pre-position adds in one or more kinds of cationic presomas in radial directions；It adds in simultaneously under certain condition One or more kinds of anion presomas, make cationic presoma with anion presoma react to be formed it is nano combined Material, and the glow peak wavelength of the nanocomposite occur during the reaction blue shift, red shift and it is constant in one kind Or it is several, it is distributed so as to fulfill in the alloy compositions of pre-position.
2. the preparation method of nanocomposite according to claim 1, which is characterized in that be pre-positioned in radial directions It puts place and adds in a kind of cationic presoma；Add in two kinds of anion forerunners with differential responses activity simultaneously under certain condition Body makes cationic presoma react forming nanocomposite with anion presoma, and the nanocomposite Glow peak wavelength occur blue shift, red shift and one or more of constant during the reaction, so as to fulfill in precalculated position The alloy compositions distribution at place.
3. the preparation method of nanocomposite according to claim 1, which is characterized in that be pre-positioned in radial directions It puts place and adds in two kinds of cationic presomas with differential responses activity；Add in a kind of anion forerunner simultaneously under certain condition Body makes cationic presoma react forming nanocomposite with anion presoma, and the nanocomposite Glow peak wavelength occur blue shift, red shift and one or more of constant during the reaction, so as to fulfill in precalculated position The alloy compositions distribution at place.
4. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite There is continuous blue shift during the reaction in glow peak wavelength.
5. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite There is alternate blue shift and constant during the reaction in glow peak wavelength.
6. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite There is alternate blue shift and red shift during the reaction in glow peak wavelength.
7. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite There is the blue shift being interrupted during the reaction in glow peak wavelength.
8. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite There is the red shift being interrupted during the reaction in glow peak wavelength.
9. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite First there is blue shift during the reaction in glow peak wavelength, then constant.
10. the preparation method of nanocomposite according to claim 1, which is characterized in that the nanocomposite Glow peak wavelength occur continuous red shift during the reaction.
11. the preparation method of nanocomposite according to claim 1, which is characterized in that the cation presoma Presoma including Zn, the presoma of the Zn is zinc methide, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, bromine Change in zinc, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate or zinc sulfate It is at least one.
12. the preparation method of nanocomposite according to claim 1, which is characterized in that the cation presoma Presoma including Cd, the presoma of the Cd is dimethyl cadmium, diethyl cadmium, cadmium acetate, acetylacetone,2,4-pentanedione cadmium, cadmium iodide, bromine At least one of cadmium, caddy, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate or cadmium sulfate.
13. the preparation method of nanocomposite according to claim 1, which is characterized in that in a heated condition simultaneously Add in one or more kinds of anion presomas.
14. the preparation method of nanocomposite according to claim 13, which is characterized in that the anion presoma Presoma including Se, the presoma of the Se is Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA, Se-ODA, Se- At least one of TOA, Se-ODPA or Se-OLA.
15. the preparation method of nanocomposite according to claim 13, which is characterized in that the anion presoma Presoma including S, the presoma of the S is S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, At least one of S-OLA or alkyl hydrosulfide.
16. the preparation method of nanocomposite according to claim 13, which is characterized in that the anion presoma Presoma including Te, the presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te- At least one of TOA, Te-ODPA or Te-OLA.
17. the preparation method of nanocomposite according to claim 13, which is characterized in that heating temperature is at 100 DEG C To between 400 DEG C.
18. the preparation method of nanocomposite according to claim 13, which is characterized in that heating time in 2s extremely Between for 24 hours.
19. the preparation method of nanocomposite according to claim 1, which is characterized in that cationic presoma and the moon The molar feed ratio of ion presoma is 100:1 to 1:Between 50.
20. a kind of nanocomposite, which is characterized in that the nanocomposite is used as described in claim 1 ~ 19 is any Preparation method be prepared.
21. a kind of semiconductor devices, which is characterized in that including nanocomposite as claimed in claim 20.
22. semiconductor devices according to claim 21, which is characterized in that the semiconductor devices is electroluminescent cell In part, photo luminescent devices, solar cell, display device, photodetector, bioprobe and device for non-linear optical Any one.
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