CN108269891B - Nano composite material, preparation method and semiconductor device - Google Patents

Nano composite material, preparation method and semiconductor device Download PDF

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CN108269891B
CN108269891B CN201611259353.9A CN201611259353A CN108269891B CN 108269891 B CN108269891 B CN 108269891B CN 201611259353 A CN201611259353 A CN 201611259353A CN 108269891 B CN108269891 B CN 108269891B
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precursor
cadmium
quantum dot
composite material
zinc
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CN108269891A (en
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杨一行
刘政
钱磊
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TCL Technology Group Co Ltd
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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 invention discloses a nano composite material, a preparation method and a semiconductor device, wherein the method comprises the following steps: adding one or more than one cation precursor at a preset position in the radial direction; and simultaneously adding one or more than one anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position. The nano composite material prepared by the preparation method not only realizes the higher-efficiency nano composite material luminous efficiency, but also can meet the comprehensive performance requirements of semiconductor devices and corresponding display technologies on the nano composite material, and is an ideal quantum dot luminous material suitable for the semiconductor devices and the display technologies.

Description

Nano composite material, preparation method and semiconductor device
Technical Field
The invention relates to the field of quantum dots, in particular to a nano composite material, a preparation method and a semiconductor device.
Background
The quantum dot is a special material which is limited to the nanometer order of magnitude in three dimensions, and the remarkable quantum confinement effect enables the quantum dot to have a plurality of unique nanometer properties: the emission wavelength is continuously adjustable, the light-emitting wavelength is narrow, the absorption spectrum is wide, the light-emitting intensity is high, the fluorescence lifetime is long, the biocompatibility is good, and the like. The characteristics enable the quantum dots to have wide application prospects in the fields of flat panel display, solid-state illumination, photovoltaic solar energy, biological markers and the like. Especially in the application of flat panel display, Quantum dot light-emitting diode (QLED) devices based on Quantum dot materials have shown great potential in the aspects of display image quality, device performance, manufacturing cost, etc. by virtue of the characteristics and optimization of Quantum dot nanomaterials. Although the performance of the QLED device in various aspects is improved in recent years, the gap between the basic device performance parameters such as device efficiency and device operation stability is still comparable to the requirement of industrial application, which also greatly hinders the development and application of the quantum dot electroluminescent display technology. In addition, not only the QLED device, but also in other fields, the characteristics of the quantum dot material relative to the conventional materials are being emphasized, for example, a photoluminescent device, a solar cell, a display device, a photodetector, a biological probe, a nonlinear optical device, and the like, and the following description will be given only by taking the QLED device as an example.
Although quantum dots have been researched and developed as a classical nano material for more than 30 years, the research time for utilizing the excellent luminescent properties of quantum dots and applying the quantum dots as a quantum dot composite material in QLED devices and corresponding display technologies is still short; therefore, at present, most of the developments and researches of the QLED devices are based on the quantum dot materials of the existing classical structural systems, and the screening and optimization criteria of the corresponding quantum dot materials are still basically based on the self-luminescence properties of the quantum dots, such as the luminescence peak width of the quantum dots, the solution quantum yield and the like. The quantum dots are directly applied to the QLED device structure so as to obtain corresponding device performance results.
However, as a set of complex optoelectronic device systems, the QLED device and the corresponding display technology have many factors that affect the performance of the device. Starting with quantum dot materials as core light-emitting layer materials alone, the quantum dot performance index required for balancing is much more complex.
Firstly, quantum dots exist in a form of a solid film of a quantum dot light emitting layer in a QLED device, so that various luminescent performance parameters originally obtained in a solution of a quantum dot material show obvious differences after the solid film is formed: for example, the emission peak wavelength in the solid thin film is red-shifted (shifted to a long wavelength), the emission peak width is increased, and the quantum yield is reduced to various degrees, that is, the excellent emission performance of the quantum dot material in the solution cannot be completely inherited to the quantum dot solid thin film of the QLED device. Therefore, when the structure and the synthesis formula of the quantum dot material are designed and optimized, the optimization of the luminous performance of the quantum dot material and the inheritance maximization of the luminous performance of the quantum dot material in a solid thin film state need to be considered at the same time.
And secondly, the light emission of the quantum dot material in the QLED device is realized by electric excitation, namely holes and electrons are respectively injected from the anode and the cathode of the QLED device through electrification, and the holes and the electrons are transmitted through corresponding functional layers in the QLED device and are recombined in a quantum dot light-emitting layer, and then photons are emitted in a radiation transition mode, so that the light emission is realized. From the above process, it can be seen that the light emitting performance of the quantum dot itself, such as the light emitting efficiency, only affects the efficiency of the radiative transition in the above process, and the overall light emitting efficiency of the QLED device is also affected by the charge injection and transport efficiency of the holes and electrons in the quantum dot material, the relative charge balance of the holes and electrons in the quantum dot material, the recombination region of the holes and electrons in the quantum dot material, and the like. Therefore, when designing and optimizing the structure of the quantum dot material, especially the fine core-shell nanostructure of the quantum dot, the electrical properties of the quantum dot after forming the solid film need to be considered in an important way: such as charge injection and conduction properties of the quantum dots, fine band structure of the quantum dots, exciton lifetime of the quantum dots, and the like.
Finally, considering that QLED devices and corresponding display technologies will not be prepared by solution methods, such as inkjet printing, which have great production cost advantages in the future, material design and development of quantum dots requires consideration of the processability of quantum dot solutions, such as the dispersibility and solubility of quantum dot solutions or printing inks, colloidal stability, print film forming properties, and the like. Meanwhile, the development of quantum dot materials is coordinated with other functional layer materials of the QLED device and the overall preparation process flow and requirements of the device.
In a word, the conventional quantum dot structure design only considering the improvement of the self-luminous performance of the quantum dot cannot meet the comprehensive requirements of the QLED device and the corresponding display technology on the quantum dot material in various aspects such as optical performance, electrical performance, processing performance and the like. The fine core-shell structure, components, energy level and the like of the quantum dot composite material need to be customized according to the requirements of the QLED device and the corresponding display technology.
Due to the high surface atomic ratio of the quantum dots, atoms that do not form non-covalent bonds (Dangling bonds) with surface ligands (Ligand) will exist in a surface defect state that will cause transitions in non-radiative pathways such that the luminescent quantum yield of the quantum dots is greatly reduced. In order to solve the problem, a semiconductor shell layer containing another semiconductor material can be grown on the surface of the outer layer of the original quantum dot to form a core-shell structure of the quantum dot, so that the luminous performance of the quantum dot can be obviously improved, and the stability of the quantum dot is improved.
The quantum dot material applicable to the development of the high-performance QLED device is mainly a quantum dot with a core-shell structure, the core and shell components of the quantum dot are respectively fixed, and the core shell has a definite boundary. Such as quantum dots with a CdSe/ZnS core-shell structure (J. Phys. chem., 1996, 100 (2), 468-471), quantum dots with a CdSe/CdS core-shell structure (J. Am. chem. Soc. 1997, 119, (30), 7019-7029), quantum dots with a CdS/ZnS core-shell structure, quantum dots with a CdS/CdSe/CdS core + multilayer shell structure (Patent US 7,919,012B 2), quantum dots with a CdSe/CdS/ZnS core + multilayer shell structure (J. Phys. chem. B, 2004, 108 (49), 18826-18831) and the like. In these quantum dots of the core-shell structure, generally speaking, the composition components of the core and the shell are fixed and different, and are generally a binary compound system composed of one kind of cation and one kind of anion. In this structure, since the growth of the core and the shell is independently and separately performed, the boundary between the core and the shell is definite, i.e., the core and the shell can be distinguished. The development of the core-shell structure quantum dot greatly improves the luminous quantum efficiency, monodispersity and quantum dot stability of the original single-component quantum dot.
Although the quantum dot performance of the quantum dot with the core-shell structure is partially improved, the luminescent performance is still to be improved from the design idea and the optimization scheme or based on the aspect of improving the luminous efficiency of the quantum dot, and in addition, the special requirements of the semiconductor device on other aspects of the quantum dot material are not comprehensively considered.
Therefore, the above-described technology is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a nanocomposite, a preparation method and a semiconductor device, and aims to solve the problems that the luminescent performance of the quantum dot material prepared by the existing preparation method needs to be improved and the requirements of the semiconductor device on the nanocomposite cannot be met.
The technical scheme of the invention is as follows:
a method of preparing a nanocomposite, comprising the steps of:
adding one or more than one cation precursor at a preset position in the radial direction; and simultaneously adding one or more than one anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
The preparation method of the nano composite material comprises the following steps of adding a cation precursor at a preset position in the radial direction; under a certain condition, two anion precursors with different reaction activities are simultaneously added, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
The preparation method of the nano composite material comprises the following steps of adding two cationic precursors with different reactivity at preset positions in the radial direction; and simultaneously adding an anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material is continuously blue-shifted in the reaction process.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material is alternately blue-shifted and unchanged in the reaction process.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material is alternately blue-shifted and red-shifted in the reaction process.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material generates discontinuous blue shift in the reaction process.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material is discontinuously red-shifted in the reaction process.
The preparation method of the nano composite material comprises the steps of firstly realizing blue shift in the luminescence peak wavelength of the nano composite material in the reaction process, and then keeping the luminescence peak wavelength unchanged.
The preparation method of the nano composite material is characterized in that the wavelength of the luminescence peak of the nano composite material is continuously red-shifted in the reaction process.
The preparation method of the nanocomposite comprises the step of preparing a cation precursor, wherein the cation precursor comprises a Zn precursor, and the Zn precursor is at least one of dimethyl zinc, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate or zinc sulfate.
The preparation method of the nano composite material comprises the step of preparing a cation precursor, wherein the cation precursor comprises a precursor of Cd, and the precursor of Cd is at least one of dimethyl cadmium, diethyl cadmium, cadmium acetate, cadmium acetylacetonate, cadmium iodide, cadmium bromide, cadmium chloride, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate or cadmium sulfate.
The preparation method of the nano composite material comprises the step of simultaneously adding one or more than one anionic precursor under the heating condition.
The preparation method of the nano composite material comprises the following step of preparing an anion precursor of Se, wherein the precursor of Se is at least one of Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
The preparation method of the nano composite material comprises the following step of preparing an anion precursor, wherein the anion precursor comprises a precursor of S, and the precursor of S is at least one of S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl mercaptan.
The preparation method of the nano composite material comprises the following step of preparing an anion precursor, wherein the anion precursor comprises a precursor of Te, and the precursor of Te is at least one of Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
The preparation method of the nano composite material comprises the step of heating at a temperature of between 100 and 400 ℃.
The preparation method of the nano composite material comprises the step of heating for 2s to 24 h.
The preparation method of the nano composite material comprises the step of mixing a cation precursor and an anion precursor according to a molar ratio of 100:1 to 1: 50.
A nanocomposite, wherein the nanocomposite is prepared by the preparation method.
A semiconductor device comprising a nanocomposite material as described above.
The semiconductor device is any one of an electroluminescent device, a photoluminescent device, a solar cell, a display device, a photoelectric detector, a biological probe and a nonlinear optical device.
Has the advantages that: the nano composite material prepared by the preparation method not only realizes higher-efficiency nano composite material luminous efficiency, but also can meet the comprehensive performance requirements of semiconductor devices and corresponding display technologies on the nano composite material, and is an ideal quantum dot luminous material suitable for the semiconductor devices and the display technologies.
Drawings
FIG. 1 is a diagram showing the energy level structure curve of a specific structure 1 of a nanocomposite material according to the present invention.
FIG. 2 is a graph of the energy level structure of a specific structure 2 of a nanocomposite material according to the present invention.
FIG. 3 is a graph of the energy level structure of a specific structure 3 of a nanocomposite material according to the present invention.
FIG. 4 is a graph of the energy level structure of a specific structure 4 of a nanocomposite material according to the present invention.
FIG. 5 is a graph of the energy level structure of a particular structure 5 of a nanocomposite material according to the invention.
FIG. 6 is a graph of the energy level structure of a nanocomposite material embodiment 6 of the present invention.
FIG. 7 is a graph of the energy level structure of a nanocomposite embodiment 7 of the present invention.
Fig. 8 is a graph of the emission peak wavelength of the quantum dot according to example 10 of the present invention.
Fig. 9 is a graph of the emission peak wavelength of the quantum dot according to example 11 of the present invention.
Fig. 10 is a graph of the emission peak wavelength of the quantum dot according to example 12 of the present invention.
Fig. 11 is a schematic structural diagram of a quantum dot light emitting diode in embodiment 33 of the present invention.
Fig. 12 is a schematic structural diagram of a quantum dot light emitting diode in embodiment 34 of the present invention.
Fig. 13 is a schematic structural diagram of a quantum dot light-emitting diode in embodiment 35 of the present invention.
Fig. 14 is a schematic structural diagram of a quantum dot light emitting diode in embodiment 36 of the present invention.
Fig. 15 is a schematic structural diagram of a quantum dot light-emitting diode in embodiment 37 of the present invention.
Fig. 16 is a schematic structural diagram of a quantum dot light emitting diode in embodiment 38 of the present invention.
Detailed Description
The present invention provides a nanocomposite, a method for preparing the same, and a semiconductor device, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a nano composite material, which comprises the following steps: adding one or more than one cation precursor at a preset position in the radial direction; and simultaneously adding one or more than one anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
Preferably, a cation precursor is added at a predetermined position in the radial direction; under a certain condition, two anion precursors with different reaction activities are simultaneously added, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
Preferably, two kinds of cation precursors having different reactivity are added at predetermined positions in the radial direction; and simultaneously adding an anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
The invention directly controls the addition of cation precursor and anion precursor of the alloy component to be synthesized at the preset position to react to form the nano composite material, thereby realizing the distribution of the alloy component required by the invention. The reaction principle is that a cation precursor with high reaction activity and an anion precursor react firstly to form a first compound, the cation precursor with low reaction activity and the anion precursor react later to form a second compound, and in the reaction process, cation exchange reaction occurs between the two compounds formed by the successive reaction, so that the distribution of the alloy components required by the invention is realized.
The first compound and the second compound can be binary or more compounds.
The nano composite material prepared by the invention comprises at least one quantum dot structural unit which is sequentially arranged in the radial direction, wherein the quantum dot structural unit is a gradient alloy component structure with energy level width changing in the radial direction or a uniform component structure with consistent energy level width in the radial direction.
That is to say, in the nano composite material prepared by the invention, a single atomic layer or more than one single atomic layer at any position in the radial direction from inside to outside in each quantum dot structural unit has a structure with an alloy component.
Further, in the present invention, the quantum dot structural unit includes group II and group VI elements. The group II elements include, but are not limited to, Zn, Cd, Hg, Cn, and the like; the group VI elements include, but are not limited to, O, S, Se, Te, Po, Lv, and the like. Specifically, the alloy composition of each quantum dot structural unit is CdxZn1-xSeyS1-yWherein x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, and x and y are not 0 and not 1 at the same time. It is noted that the above is preferable, and for the quantum dot structural unit of the graded alloy composition structure, the compositions are all alloy compositions; while the component of the quantum dot structural unit with the uniform component structure can be an alloy component or a non-alloy component, the invention preferably relates to an alloy component, namely the uniform component structure is a uniform alloy component structure, more preferably comprises group II and group VI elements, and the subsequent embodiments of the invention are described by taking the uniform alloy component structure as an example, but obviously, the invention can also be carried out on the non-alloy uniform component structure.
The radial direction herein refers to a direction outward from the center of the nanocomposite, for example, assuming that the nanocomposite of the present invention is a spherical or spheroidal structure, the radial direction refers to a direction along a radius, the center (or inner) of the nanocomposite refers to the center of its physical structure, and the surface (or outer) of the nanocomposite refers to the surface of its physical structure.
The structure of the nanocomposite material of the invention is described in detail below:
specifically, the luminescence peak wavelength of the nanocomposite material exhibits a continuous blue shift during the reaction to achieve a graded alloy composition distribution at a specified position. The occurrence of the blue shift represents that the emission peak is shifted to a short wavelength direction and the energy level width is widened, as shown in fig. 1, in the radial direction of the quantum dot, the energy level width of the structural unit of the quantum dot is widened (continuous blue shift).
Specifically, as shown in fig. 1, the nanocomposite with a funnel-type energy level structure is prepared, and the energy level width corresponding to the composition of the quantum dot structural unit alloy inside the nanocomposite is smaller than the energy level width corresponding to the composition of the quantum dot structural unit alloy outside the nanocomposite; specifically, the nano composite material provided by the invention comprises at least one quantum dot structural unit which is sequentially arranged in the radial direction, wherein the quantum dot structural unit is a gradually-changed alloy component structure of which the energy level width is wider towards the outside in the radial direction, and the energy levels of the quantum dot structural units of the gradually-changed alloy component structures adjacent to each other in the radial direction are continuous; the structure of the nanocomposite shown in fig. 1 in the subsequent examples is referred to as a specific structure 1. In the nanocomposite material in fig. 1, the energy level widths of the respective adjacent quantum dot structural units have a continuous structure, that is, the energy level widths of the respective adjacent quantum dot structural units have a continuously changing characteristic, but not an abrupt structure, that is, the alloy components of the quantum dots also have continuity, and the principle of the subsequent continuous structure is the same.
Further, in the quantum dot structural units adjacent in the radial direction, the energy level width of the quantum dot structural unit close to the center is smaller than that of the quantum dot structural unit far from the center; that is, in the nanocomposite, the energy level width from the center to the surface is gradually widened, thereby forming a funnel-type structure with a gradually enlarged opening, wherein the gradually enlarged opening means that the energy level from the center of the nanocomposite to the surface of the nanocomposite is continuous in the energy level structure shown in fig. 1. Meanwhile, in the nano composite material, the energy levels of all the adjacent quantum dot structural units are continuous, namely the synthetic components of the quantum dots also have the characteristic of continuous change, and the characteristic is more favorable for realizing high luminous efficiency.
That is, the specific structure 1 of the nanocomposite material is a quantum dot structure having a continuously graded alloy composition in the radial direction from the inside to the outside; the quantum dot structure has the characteristic of continuous change along the radial direction from inside to outside in the composition; correspondingly, the energy level distribution also has the characteristic of continuous change along the radial direction from inside to outside; the quantum dot structure has the characteristic of continuous change in composition and energy level distribution, and compared with the relation between a quantum dot core and a quantum dot shell with clear boundaries, the nano composite material disclosed by the invention is not only beneficial to realizing more efficient luminous efficiency, but also can meet the comprehensive performance requirements of a semiconductor device and a corresponding display technology on the nano composite material, and is an ideal quantum dot luminous material suitable for the semiconductor device and the display technology.
Further, in the nanocomposite provided in FIG. 1, the alloy component at the point A is Cdx0 AZn1-x0 ASey0 AS1-y0 AThe alloy component at the B point is Cdx0 BZn1-x0 BSey0 BS1-y0 BWherein point a is closer to the nanocomposite center than point B, and the composition of points a and B satisfies:x0 A>x0 B，y0 A >y0 B. That is, for any two points in the nanocomposite, point A and point B, with point A being closer to the nanocomposite center than point B, thenx0 A>x0 B，y0 A >y0 BI.e. the Cd content at point A is greater than that at point BThe content of Cd is less than that of Zn at the point A, the content of Se at the point A is more than that of Se at the point B, and the content of S at the point A is less than that of S at the point B. Thus, in the nanocomposite, a graded structure is formed in the radial direction, and since the Cd and Se contents are lower the further outward (i.e., away from the nanocomposite center) in the radial direction, and the Zn and S contents are higher, the energy level width thereof will be wider according to the characteristics of these elements.
In the subsequent nano composite materials with different specific structures, if the quantum dot structural unit has a gradually-changed alloy component structure with the energy level width wider towards the outside in the radial direction, the alloy components are preferably Cdx0Zn1-x0Sey0S1-y0Wherein the alloy component of the point A is Cdx0 AZn1-x0 ASey0 AS1-y0 AThe alloy component at the B point is Cdx0 BZn1-x0 BSey0 BS1-y0 BWherein point a is closer to the nanocomposite center than point B, and the composition of points a and B satisfies:x0 A>x0 B，y0 A >y0 B. If the quantum dot structural unit is a gradual change alloy component structure with the energy level width being narrower towards the outside in the radial direction, the alloy components are preferably Cdx0Zn1- x0Sey0S1-y0Wherein the alloy component of the C point is Cdx0 CZn1-x0 CSey0 CS1-y0 CThe alloy component at the D point is Cdx0 DZn1- x0 DSey0 DS1-y0 DWherein point C is closer to the nanocomposite center than point D, and the composition of points C and D satisfies:x0 C＜x0 D，y0 C＜y0 D. If the quantum dot structural unit has a uniform alloy component structure (i.e., the energy level widths in the radial direction are consistent), the alloy components are preferably Cdx0Zn1-x0Sey0S1-y0Wherein the alloy component of the E point is Cdx0 EZn1-x0 ESey0 ES1-y0 EThe alloy component of F point is Cdx0 FZn1-x0 FSey0 FS1-y0 FWherein point E is closer to the nanocomposite center than point F, and the composition of points E and F satisfies:x0 E=x0 F，y0 E=y0 F。
specifically, the luminous peak wavelength of the nano composite material is alternately blue-shifted and unchanged in the reaction process. The occurrence of a blue shift indicates that the emission peak shifts in the short-wave direction and the energy level width widens, the occurrence of a red shift indicates that the emission peak shifts in the long-wave direction and the energy level width narrows, and the occurrence of a red shift indicates that the energy level width does not change if the wavelength of the emission peak does not change. The occurrence of the alternating blue shift and the invariant represents that the energy level widths are alternately changed, that is, as shown in fig. 2, in the radial direction of the quantum dot, the energy level width is widened (blue shift) in the first interval, the energy level width is unchanged (invariant) in the second interval, and the energy level width is widened (blue shift) in the third interval.
Specifically, as shown in fig. 2, the present invention also prepares a nanocomposite having quantum dot structural units in which the energy level width corresponding to the internal alloy composition is not greater than the energy level width corresponding to the external alloy composition, and at least one layer of uniform alloy composition structure is contained between the centermost region and the outmost region of the quantum dot structure; that is to say, the nanocomposite provided by the invention comprises at least three quantum dot structural units sequentially arranged in the radial direction, wherein, of the at least three quantum dot structural units, the quantum dot structural units positioned in the center and on the surface are all gradient alloy component structures with wider energy level widths towards the outside in the radial direction, the energy levels of the quantum dot structural units of the adjacent gradient alloy component structures in the radial direction are continuous, and one quantum dot structural unit positioned between the quantum dot structural units in the center and on the surface is a uniform alloy component structure. The structure of the nanocomposite shown in fig. 2 is referred to as a specific structure 2 in the subsequent examples.
Specifically, as shown in the nanocomposite provided in fig. 2, the alloy component at any point is Cd on the quantum dot structural unit of a layer of uniform alloy component structure between the quantum dot structural units at the center and the surfacex1Zn1-x1Sey1S1-y1Wherein 0. ltoreq. x 1. ltoreq.1, 0. ltoreq. y 1. ltoreq.1, and x1 and y1 are not 0 at the same time and not 1 at the same time, and x1 and y1 are fixed values. For example, Cd as the alloy component at a certain point0.5Zn0.5Se0.5S0.5And the alloy component at another point in the radial direction should also be Cd0.5Zn0.5Se0.5S0.5(ii) a For example, the uniform component at a certain point in a quantum dot structural unit of a certain uniform alloy component structure is Cd0.7Zn0.3S, and the alloy component of another point in the quantum dot structural unit is Cd0.7Zn0.3S; for example, the uniform alloy composition at one point in the quantum dot unit of a uniform alloy composition structure is CdSe, and the alloy composition at another point in the quantum dot unit is CdSe.
Further, in the nanocomposite provided in fig. 2, the quantum dot structural units located at the center and the surface are all gradient alloy component structures whose energy level widths are wider toward the outside in the radial direction, and the energy levels of the quantum dot structural units of adjacent gradient alloy component structures in the radial direction are continuous; that is, in the quantum dot structural unit with the gradually-changed alloy component structure, the energy level width corresponding to the alloy composition at any point in the radial direction is larger than the energy level width corresponding to the alloy composition adjacent to another point closer to the center of the quantum dot structure. The alloy component in the quantum dot structural unit with the gradually-changed alloy component structure is Cdx2Zn1-x2Sey2S1-y2Wherein x2 is not less than 0 and not more than 1, y2 is not less than 1 and x2 and y2 are not 0 and not 1 at the same time. For example, Cd as the alloy component at a certain point0.5Zn0.5Se0.5S0.5And the other alloy component is Cd0.3Zn0.7Se0.4S0.6。
Specifically, the luminescence peak wavelength of the nanocomposite material undergoes alternating blue-shift and red-shift during the reaction to achieve a graded alloy composition distribution at a specified position. The occurrence of blue shift represents that the band moves towards the short wave direction, the energy level width is widened, the occurrence of red shift represents that the luminescence peak moves towards the long wave direction, the energy level width is narrowed, and if the wavelength of the luminescence peak is not changed, the energy level width is not changed. The occurrence of the alternating blue-shift and red-shift represents that the energy level widths are alternately changed, that is, as shown in fig. 3, in the radial direction of the quantum dot, the energy level width is widened (blue-shift) in the first interval, narrowed (red-shift) in the second interval, widened (blue-shift) in the third interval, narrowed (red-shift) in the fourth interval, and widened (blue-shift) in the fifth interval.
Specifically, as shown in fig. 3, the present invention also prepares a nanocomposite having a fully graded alloy composition with a quantum well structure; that is, the present invention provides a nanocomposite including two types of quantum dot structural units (a 1 type and a2 type), wherein the quantum dot structural unit of the a1 type is a graded alloy composition structure in which the energy level width is wider toward the outside in the radial direction, and the quantum dot structural unit of the a2 type is a graded alloy composition structure in which the energy level width is narrower toward the outside in the radial direction, the two types of quantum dot structural units are alternately distributed in the radial direction in order, and the energy levels of the quantum dot structural units adjacent in the radial direction are continuous. That is, the quantum dot structural unit distribution of the nanocomposite may be: a1, A2, A1, A2 and A1 … can also be A2, A1, A2, A1 and A2 …, namely the initial quantum dot structural unit can be of an A1 type or an A2 type. In the quantum dot structural unit of a1 type, the energy level width is wider as going outward, and in the quantum dot structural unit of a2 type, the energy level width is narrower as going outward, both energy level structures extend in the radial direction like a wavy line, and the structure of the nanocomposite shown in fig. 3 is referred to as a specific structure 3 in the subsequent examples.
Specifically, the luminescence peak wavelength of the nanocomposite material exhibits an intermittent blue shift during the reaction. The occurrence of blue shift represents that the luminescence peak is shifted to the short wave direction and the energy level width is widened. Of course, the red shift of the emission peak wavelength means that the emission peak shifts in the long-wavelength direction and the energy level width becomes narrower, while the unchanged emission peak wavelength means that the energy level width does not change. The appearance of discontinuous blue shift means that the energy level width between the quantum dot structural units is changed abruptly rather than continuously, i.e. as shown in fig. 4.
Specifically, as shown in fig. 4, the nanocomposite of the alloy component of the quantum well structure with the energy level mutation is further prepared, specifically, the quantum dot structure units are all gradient alloy component structures with the wider energy level width outward in the radial direction, and the energy levels of the adjacent quantum dot structure units are discontinuous, that is, the energy level widths of the adjacent quantum dot structure units have the characteristic of discontinuous change, that is, the mutation characteristic, that is, the alloy component of the quantum dot also has the mutation property, and the subsequent mutation structure principle is the same; the structure of the nanocomposite shown in fig. 4 is referred to as a specific structure 4 in the subsequent examples.
Specifically, the nanocomposite shown in fig. 4 is formed by sequentially arranging a plurality of quantum dot structural units in an abrupt change manner, and the quantum dot structural units are all gradient alloy component structures with wider energy level widths outward in the radial direction. Further, in the nano composite material, the energy level width of the quantum dot structural unit close to the center is smaller than that of the quantum dot structural unit far away from the center. That is, in the nanocomposite, the energy level width from the center to the surface is gradually widened, so as to form a funnel-type structure with a discontinuous opening gradually enlarged, but of course, the nanocomposite is not limited to the above manner, that is, the energy level width of the quantum dot structure unit far away from the center may be smaller than that of the quantum dot structure unit near the center, and in this structure, the energy level widths of the adjacent quantum dot structure units overlap in a staggered manner.
Specifically, the luminescence peak wavelength of the nanocomposite material shows an intermittent red shift during the reaction. The red shift represents that the light-emitting peak moves towards the long-wave direction and the energy level width is narrowed. When the wavelength of the luminescence peak appears blue shift, the luminescence peak moves to the short wave direction, the energy level width is widened, and when the wavelength of the luminescence peak is not changed, the energy level width is not changed. The discontinuous red shift represents that the energy level width between the quantum dot structural units is changed abruptly instead of continuously, i.e. as shown in fig. 5.
Specifically, as shown in fig. 5, another nanocomposite of an alloy component having a quantum well structure with a sudden change in energy level is prepared, specifically, the quantum dot structure units are all gradually-changed alloy component structures with narrower energy level widths outward in the radial direction, and the energy levels of the adjacent quantum dot structure units are discontinuous, that is, the energy level widths of the adjacent quantum dot structure units have a characteristic of discontinuous change, that is, a sudden change characteristic, that is, the alloy component of the quantum dot also has a sudden change property, and the subsequent sudden change structure principle is the same; the structure of the nanocomposite shown in fig. 5 is referred to as a specific structure 5 in the subsequent examples.
Specifically, the nanocomposite shown in fig. 5 is formed by sequentially arranging a plurality of quantum dot structural units in an abrupt change manner, and the quantum dot structural units are all gradient alloy component structures with narrower energy level widths outward in the radial direction. Further, in the nano composite material, the energy level width of the quantum dot structural unit close to the center is larger than that of the quantum dot structural unit far away from the center. That is, in the nanocomposite, the energy level width from the center to the surface is gradually narrowed, so as to form a funnel-type structure with a discontinuous opening which is gradually narrowed, but of course, the nanocomposite is not limited to the above manner, that is, the energy level width of the quantum dot structure unit far away from the center may be larger than that of the quantum dot structure unit near the center, and in such a structure, the energy level widths of the adjacent quantum dot structure units are overlapped in a staggered manner.
Specifically, the wavelength of the luminescence peak of the nanocomposite material firstly shows a blue shift in the reaction process and then does not change. The occurrence of the blue shift indicates that the emission peak shifts in the short-wavelength direction and the level width becomes wider, and if the emission peak wavelength does not change, the level width does not change, that is, as shown in fig. 6, the level width becomes wider (blue shift) in the first interval and the level width does not change (does not change) in the second interval in the radial direction of the quantum dot.
Specifically, as shown in fig. 6, the present invention also prepares a nanocomposite material, the energy level width of the alloy composition in the nanocomposite material becomes gradually larger from the center to the outside, and the outermost region of the quantum dot structure is a uniform alloy composition; specifically, the nanocomposite comprises two kinds of quantum dot structural units (A3 type and a4 type), wherein the quantum dot structural unit of the A3 type is a graded alloy composition structure in which the energy level width is wider outward in the radial direction, the quantum dot structural unit of the a4 type is a uniform alloy composition structure, the interior of the nanocomposite comprises quantum dot structural units comprising one or more graded alloy composition structures, and the energy levels of the quantum dot structural units of the graded alloy composition structures adjacent in the radial direction are continuous; the outside of the nano composite material comprises one or more quantum dot structural units with uniform alloy component structures; the structure of the nanocomposite shown in fig. 6 is referred to as a specific structure 6 in the subsequent examples.
Specifically, in the nanocomposite material shown in fig. 6, the distribution of the quantum dot structural units is A3 … A3a4 … a4, that is, the inside of the nanocomposite material is composed of the A3 type quantum dot structural units, the outside of the nanocomposite material is composed of the a4 type quantum dot structural units, and the number of the A3 type quantum dot structural units and the number of the a4 type quantum dot structural units are both greater than or equal to 1.
Further, the luminescence peak wavelength of the nanocomposite material shows a continuous red shift during the reaction. The red shift represents that the light-emitting peak moves towards the long-wave direction and the energy level width is narrowed. When the wavelength of the luminescence peak appears blue shift, the luminescence peak moves to the short wave direction, the energy level width is widened, and when the wavelength of the luminescence peak is not changed, the energy level width is not changed. The occurrence of the red shift represents that the emission peak is shifted to the long wavelength direction and the energy level width is narrowed, as shown in fig. 7, in the radial direction of the quantum dot, the energy level width of the structural unit of the quantum dot is narrowed (red shift).
Specifically, as shown in fig. 7, another nanocomposite material is prepared according to the present invention, wherein the energy level widths of the alloy components located inside the nanocomposite material are uniform, and the energy level widths of the alloy components located outside the quantum dots are gradually increased from the center to the outside; specifically, the nano composite material comprises two quantum dot structural units (A5 type and A6 type), wherein the A5 type quantum dot structural unit is of a uniform alloy component structure, the A6 type quantum dot structural unit is of a gradual change alloy component structure with wider energy level width towards the outside in the radial direction, and the inside of the nano composite material comprises one or more quantum dot structural units of the uniform alloy component structure; the outside of the nano composite material comprises one or more quantum dot structural units of the gradually-changed alloy composition structure, and the energy levels of the quantum dot structural units of the gradually-changed alloy composition structure adjacent in the radial direction are continuous; the structure of the nanocomposite shown in fig. 7 is referred to as a specific structure 7 in the subsequent examples.
Specifically, in the nanocomposite material shown in fig. 7, the distribution of the monoatomic layers thereof is A5 … A5a6 … a6, that is, the inside of the nanocomposite material is composed of A5 type quantum dot structural units, the outside of the nanocomposite material is composed of a6 type quantum dot structural units, and the number of A5 type quantum dot structural units and the number of a6 type quantum dot structural units are both 1 or more.
Further, the quantum dot structure unit provided by the invention comprises 2-20 monoatomic layers. Preferably, the quantum dot structure unit comprises 2-5 monoatomic layers, and the preferable number of layers can ensure that the quantum dot realizes good luminous quantum yield and high charge injection efficiency.
Further, the quantum dot light-emitting unit comprises 1-10 unit cell layers, preferably 2-5 unit cell layers; the unit cell layer is a minimum structure unit, namely the alloy components of the unit cell layer of each layer are fixed, namely the unit cell layer has the same lattice parameter and elements, each quantum dot structure unit is a closed unit cell curved surface formed by connecting the unit cell layers, and the energy level width between the adjacent unit cell layers has a continuous structure or a mutation structure.
The cationic precursor includes: a precursor of Zn, which is at least one of dimethyl Zinc (dimethyl Zinc), diethyl Zinc (diethyl Zinc), Zinc acetate (Zinc acetate), Zinc acetylacetonate (Zinc acetate), 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), but is not limited thereto.
The cationic precursor includes a precursor of Cd, and the precursor of Cd is at least one of cadmium dimethyl (cadmium), cadmium diethyl (cadmium), cadmium acetate (cadmium acetate), cadmium acetylacetonate (cadmium acetylacetonate), cadmium iodide (cadmium iodide), cadmium bromide (cadmium bromide), cadmium chloride (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 phosphate), cadmium sulfate (cadmium sulfate), cadmium oleate (cadmium oleate), cadmium stearate (cadmium stearate), or the like, but is not limited thereto.
The anion precursor includes a precursor of Se, for example, a compound formed by combining Se with some organic substances, and specifically, may be at least one of Se-TOP (selenium-trinuclealphosphine), Se-TBP (selenium-trinuclealphosphine), Se-TPP (selenium-trinuclealphosphine), Se-ODE (selenium-1-octadecene), Se-OA (selenium-oleic acid), Se-ODA (selenium-octadececylamine), Se-TOA (selenium-trinucleamine), Se-ODPA (selenium-octadecylphosphinic acid), Se-OLA (selenium-olylamine), and the like, but is not limited thereto.
The anion precursor includes a precursor of S, for example, a compound formed by any combination of S and some organic substances, and specifically, may be at least one of S-TOP (sulfur-trichloro-tolylphosphine), S-TBP (sulfur-tributylphosphine), S-TPP (sulfur-triphenylphosphine), S-ODE (sulfur-1-octadiene), S-OA (sulfur-oleic acid), S-ODA (sulfur-octadiene), S-TOA (sulfur-octadiene), S-ODPA (sulfur-octadiene acid), S-OLA (sulfur-oleic acid), and the like, but is not limited thereto; the precursor of S may also be alkyl thiol (alkyl thiol), which may be at least one of hexanethiol (hexanethiol), octanethiol (octanethiol), decanethiol (decanethiol), dodecanethiol (docetaethiol), hexadecanethiol (hexanetaethiol) or mercaptopropylsilane (mercaptopropylalane), etc., but is not limited thereto.
The anion precursor comprises a precursor of Te, and the precursor of Te is at least one of Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
The cation precursor and the anion precursor can be selected from one or more of the following components according to the final composition of the nano composite material: for example, synthesis of CdxZn1-xSeyS1-yThe precursor of Cd, the precursor of Zn, the precursor of Se and the precursor of S are needed in the preparation of the nano composite material; synthesis of Cd if requiredxZn1-xFor the S nanocomposite, a Cd precursor, a Zn precursor and an S precursor are required; synthesis of Cd if requiredxZn1-xIn the case of a Se nanocomposite, a precursor of Cd, a precursor of Zn, and a precursor of Se are required.
In the production method of the present invention, the cation exchange reaction is preferably carried out under conditions such that the heating reaction is carried out, for example, at a temperature of from 100 ℃ to 400 ℃, preferably at a temperature of from 150 ℃ to 380 ℃. The heating time is between 2s and 24h, and the preferable heating time is between 5min and 4 h.
The higher the heating temperature, the faster the rate of cation exchange reaction, and the larger the thickness range and exchange degree of cation exchange, but the thickness and degree range gradually reach the relative saturation degree; similarly, the longer the heating time, the greater the thickness range and degree of cation exchange, but the range of thickness and degree gradually reaches a level of relative saturation. The thickness range and extent of cation exchange directly determines the resulting graded alloy composition distribution. The distribution of the graded alloy composition formed by cation exchange is also determined by the thickness of the binary or multi-element compound nanocrystals formed by each.
The molar ratio of the cationic precursor to the anionic precursor in forming each layer of the compound is from 100:1 to 1:50 (specifically, the molar charge ratio of the cation to the anion), for example, the molar ratio of the cationic precursor to the anionic precursor in forming the first layer of the compound is from 100:1 to 1: 50; in forming the second layer of compounds, the molar ratio of the cationic precursor to the anionic precursor is from 100:1 to 1:50, preferably from 20:1 to 1:10, the preferred molar ratio of the cationic precursor to the anionic precursor providing a reaction rate in a readily controllable range.
The invention also provides a nano composite material, wherein the nano composite material is prepared by adopting the preparation method.
The nano composite material prepared by the preparation method has the luminescence peak wavelength range of 400 nm to 700 nm, the preferred luminescence peak wavelength range of 430 nm to 660 nm, and the preferred quantum dot luminescence peak wavelength range can ensure that the quantum dot can realize the luminescence quantum yield of more than 30% in the range.
The nanocomposite prepared by the above preparation method has a luminescence quantum yield ranging from 1% to 100%, preferably a luminescence quantum yield ranging from 30% to 100%, and the preferred luminescence quantum yield range can ensure good applicability of quantum dots.
Further, in the present invention, the full width at half maximum of the light emission peak of the nanocomposite material is 12 to 80 nm.
The present invention also provides a semiconductor device comprising a nanocomposite material as described above.
The semiconductor device is any one of an electroluminescent device, a photoluminescent device, a solar cell, a display device, a photoelectric detector, a biological probe and a nonlinear optical device.
Taking an electroluminescent device as an example, the invention provides a quantum dot electroluminescent device QLED taking the nano composite material as a luminescent layer material. The quantum dot electroluminescent device can realize that: 1) high efficiency charge injection, 2) high luminance, 3) low driving voltage, 4) high device efficiency, and the like. Meanwhile, the nano composite material has the characteristics of easiness in control and various performance level structures, and can fully meet and match with the energy level structures of other functional layers in the device to realize the matching of the integral energy level structure of the device, thereby being beneficial to realizing a high-efficiency and stable QLED device.
The photoluminescence device refers to a device which obtains energy by depending on an external light source for irradiation, generates excitation to cause luminescence, and can cause photoluminescence such as phosphorescence and fluorescence by ultraviolet radiation, visible light and infrared radiation. The nano crystal can be used as a luminescent material of a photoluminescence device.
The solar cell is also called a photovoltaic device, and the nanocrystal can be used as a light absorption material of the solar cell, so that various performances of the photovoltaic device are effectively improved.
The display device refers to a backlight module or a display panel using the backlight module, and the display panel can be applied to various products, such as a display, a tablet computer, a mobile phone, a notebook computer, a flat-panel television, a wearable display device or other products including display panels with different sizes.
The photoelectric detector is a device capable of converting an optical signal into an electric signal, and the principle is that the conductivity of an irradiated material is changed due to radiation, and the quantum dot material is applied to the photoelectric detector, so that the photoelectric detector has the following advantages: the optical fiber is sensitive to vertical incident light, has high photoconductive responsivity, high specific detectivity and continuously adjustable detection wavelength, and can be prepared at low temperature. In the operation process of the photoelectric detector with the structure, the photo-generated electron-hole pairs generated after the quantum dot photosensitive layer (namely the nano crystal provided by the invention) absorbs photons can be separated under the action of a built-in electric field, so that the photoelectric detector with the structure has lower driving voltage, can work under low external bias voltage even 0 external bias voltage, and is easy to control.
The biological probe is a device which modifies a certain material to enable the material to have a labeling function, for example, the nano crystal is coated to form a fluorescent probe, and the fluorescent probe is applied to the field of cell imaging or substance detection.
The nonlinear optical device belongs to the technical field of optical laser, and is widely applied, such as electro-optical switching and laser modulation, laser frequency conversion and laser frequency tuning; optical information processing is carried out, and imaging quality and light beam quality are improved; as nonlinear etalons and bistable devices; the high excited state and high resolution spectrum of the substance and the transfer process of the internal energy and excitation of the substance and other relaxation processes are researched.
Example 1: preparation of quantum dots based on CdZnSeS/CdZnSeS
Firstly, injecting a precursor of cation Cd, a precursor of cation Zn, a precursor of anion Se and a precursor of anion S into a reaction system to form CdyZn1-ySebS1-bA layer (wherein y is 0. ltoreq. y.ltoreq.1, b is 0. ltoreq. b.ltoreq.1); continuously injecting a precursor of cation Cd, a precursor of cation Zn, a precursor of anion Se and a precursor of anion S into a reaction system, wherein Cd is in a structure shown in the specificationyZn1-ySebS1-bCd formed on the surface of the layerzZn1-zSecS1-cA layer (where 0. ltoreq. z.ltoreq.1, and z is not equal to y, 0. ltoreq. c.ltoreq.1); under the reaction conditions of certain heating temperature, heating time and the like, the exchange of Cd and Zn ions in the inner and outer layer nanocrystals (namely the two-layer compound) occurs; cd is the difference between the number of cations that migrate from a first to a secondyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cA graded alloy composition distribution of Cd content and Zn content is formed near the interface of the layers, i.e. CdxZn1-xSeaS1-aWherein x is more than or equal to 0 and less than or equal to 1, and a is more than or equal to 0 and less than or equal to 1.
Example 2: preparation method of quantum dots based on CdZnS/CdZnS
Firstly, injecting a precursor of cation Cd, a precursor of cation Zn and a precursor of anion S into a reaction system to form CdyZn1-yAn S layer (wherein y is more than or equal to 0 and less than or equal to 1); continuously injecting a precursor of cation Cd, a precursor of cation Zn and a precursor of anion S into a reaction system, wherein the precursor of cation Cd, the precursor of cation Zn and the precursor of anion S are mixed to form a mixtureyZn1-yCd formed on the surface of the S layerzZn1-zAn S layer (wherein z is more than or equal to 0 and less than or equal to 1, and z is not equal to y); under the reaction conditions of certain heating temperature, heating time and the like, the exchange of Cd and Zn ions in the inner and outer layer nanocrystals (namely the two-layer compound) occurs; cd is the difference between the number of cations that migrate from a first to a secondyZn1-yS layer and CdzZn1-zThe interface of the S layer is formed with a gradual alloy component distribution of Cd content and Zn content, namely CdxZn1-xAnd S, wherein x is more than or equal to 0 and less than or equal to 1.
Example 3: preparation of quantum dots based on CdZnSe/CdZnSe
Firstly, injecting a precursor of cation Cd, a precursor of cation Zn and a precursor of anion Se into a reaction system to form CdyZn1-yA Se layer (wherein y is more than or equal to 0 and less than or equal to 1); continuously injecting a precursor of cation Cd, a precursor of cation Zn and a precursor of anion Se into a reaction system to react with the CdyZn1-yForming Cd on the surface of the Se layerzZn1-zA Se layer (wherein z is 0-1 and z is not equal to y); under the reaction conditions of certain heating temperature, heating time and the like, the exchange of Cd and Zn ions in the inner and outer layer nanocrystals occurs; cd is the difference between the number of cations that migrate from a first to a secondyZn1-ySe layer and CdzZn1-zThe gradual alloy component distribution of Cd content and Zn content is formed near the interface of the Se layer, namely CdxZn1-xSe, wherein x is more than or equal to 0 and less than or equal to 1.
Example 4: preparation based on CdS/ZnS quantum dots
Injecting a precursor of cation Cd and a precursor of anion S into a reaction system to form a CdS layer; continuously injecting a precursor of cation Zn and a precursor of anion S into the reaction system, and forming a ZnS layer on the surface of the CdS layer; under the reaction conditions of certain heating temperature, heating time and the like, Zn cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Cd cations, namely Cd ions migrate to the outer layer and exchange between Cd and Zn ions; since the migration distance of the cations is limited and the probability of migration is smaller when the migration distance is farther away, a graded alloy composition distribution in which the Cd content gradually decreases along the radial direction outwards and the Zn content gradually increases along the radial direction outwards, namely Cd is formed near the interface of the CdS layer and the ZnS layerxZn1-xS, wherein x is more than or equal to 0 and less than or equal to 1, and x is monotonically decreased from 1 to 0 from inside to outside (in the radial direction).
Example 5: preparation based on CdSe/ZnSe quantum dots
Injecting a precursor of cation Cd and a precursor of anion Se into a reaction system to form a CdSe layer; continuously injecting a precursor of cation Zn and a precursor of anion Se into the reaction system to form a ZnSe layer on the surface of the CdSe layer; under the reaction conditions of certain heating temperature, heating time and the like, Zn cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Cd cations, namely Cd ions migrate to the outer layer and exchange between Cd and Zn ions; because the migration distance of the cations is limited and the probability of migration is smaller when the migration distance is farther away, a gradient alloy component distribution that the content of Cd gradually decreases along the radial direction outwards and the content of Zn gradually increases along the radial direction outwards is formed near the interface of the CdSe layer and the ZnSe layer, namely CdxZn1-xSe, wherein x is more than or equal to 0 and less than or equal to 1, and x monotonically decreases from 1 to 0 from inside to outside (radial direction).
Example 6: preparation based on CdSeS/ZnSeS quantum dots
Firstly, injecting a precursor of cation Cd, a precursor of anion Se and a precursor of anion S into a reaction system to form CdSebS1-bA layer (wherein 0. ltoreq. b. ltoreq.1); the CdSe precursor, the anion Se precursor and the anion S precursor are injected into the reaction systembS1-bZnSe formed on the surface of the layercS1-cA layer (wherein 0. ltoreq. c. ltoreq.1); under the reaction conditions of certain heating temperature, heating time and the like, Zn cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Cd cations, namely Cd ions migrate to the outer layer and exchange between Cd and Zn ions; CdSe is a common phenomenon because the migration distance of cations is limited and the probability of migration is smaller for longer migration distancesbS1-bLayer and ZnSecS1-cA gradient alloy component distribution that the Cd content gradually decreases along the radial direction and the Zn content gradually increases along the radial direction is formed near the interface of the layers, namely CdxZn1-xSeaS1-aWherein x is more than or equal to 0 and less than or equal to 1, x is monotonically decreased from 1 to 0 from inside to outside (in the radial direction), and a is more than or equal to 0 and less than or equal to 1.
Example 7: preparation based on ZnS/CdS quantum dots
Injecting a precursor of cation Zn and a precursor of anion S into a reaction system to form a ZnS layer; continuously injecting a precursor of the cation Cd and a precursor of the anion S into the reaction system, and forming a CdS layer on the surface of the ZnS layer; under the reaction conditions of certain heating temperature, heating time and the like, Cd cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Zn cations, namely Zn ions migrate to the outer layer and exchange Cd and Zn ions; since the migration distance of the cations is limited and the probability of migration is smaller for the farther migration distance, a graded alloy composition distribution, i.e., a distribution of Cd in which the Zn content gradually decreases and the Cd content gradually increases radially outward, is formed near the interface between the ZnS layer and the CdS layerxZn1-xS, wherein x is more than or equal to 0 and less than or equal to 1, and x is from inside to outside (diameter)To the direction) monotonically increases from 0 to 1.
Example 8: preparation based on ZnSe/CdSe quantum dots
Firstly, injecting a precursor of cation Zn and a precursor of anion Se into a reaction system to form a ZnSe layer; continuously injecting a precursor of the cation Cd and a precursor of the anion Se into the reaction system to form a CdSe layer on the surface of the ZnSe layer; under the reaction conditions of certain heating temperature, heating time and the like, Cd cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Zn cations, namely Zn ions migrate to the outer layer and exchange Cd and Zn ions; because the migration distance of the cations is limited and the probability of migration is smaller when the migration distance is farther away, a gradient alloy component distribution that the Zn content is gradually reduced along the radial direction outwards and the Cd content is gradually increased along the radial direction outwards is formed near the interface of the ZnSe layer and the CdSe layer, namely CdxZn1-xSe, where x is 0. ltoreq. x.ltoreq.1 and x monotonically increases from 0 to 1 from the inside to the outside (radial direction).
Example 9: preparation of ZnSeS/CdSeS-based quantum dots
Firstly, injecting a precursor of cation Zn, a precursor of anion Se and a precursor of anion S into a reaction system to form ZnSebS1-bA layer (wherein 0. ltoreq. b. ltoreq.1); continuously injecting the precursor of the cation Cd, the precursor of the anion Se and the precursor of the anion S into the reaction system to form the CdSe on the surface of the ZnSebS1-b layercS1-cA layer (wherein 0. ltoreq. c. ltoreq.1); under the reaction conditions of certain heating temperature, heating time and the like, Cd cations on the outer layer gradually migrate to the inner layer and undergo cation exchange reaction with Zn cations, namely Zn ions migrate to the outer layer and exchange Cd and Zn ions; since the migration distance of cations is limited and the probability of migration occurring at a longer migration distance is smaller, it is in ZnSebS1-bLayer with CdSecS1-cA gradient alloy component distribution that the Zn content gradually decreases along the radial direction and the Cd content gradually increases along the radial direction is formed near the interface of the layers, namely CdxZn1-xSeaS1-aWhich isWherein x is more than or equal to 0 and less than or equal to 1, x is monotonically increased from 0 to 1 from inside to outside, and a is more than or equal to 0 and less than or equal to 1.
Example 10: blue quantum dot Cd with specific structure 1xZn1-xPreparation of S
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the precursor into a reaction system, and quickly injecting CdxZn1-xS is rapidly nucleated, and after the reaction is carried out for 10 min, 3mL of trioctylphosphine sulfide precursor and 6mL of cadmium oleate precursor are respectively injected into the reaction system at the speed of 3 mL/h and 10 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and then centrifugally purifying to obtain the blue quantum dot Cd with the funnel-type energy level structure with the gradually-enlarged openingxZn1-xS, as shown in FIG. 8, the peak wavelength of the emission was 453nm, and the absorbance gradually decreased with the increase in the wavelength.
Example 11: green quantum dot Cd with specific structure 1xZn1-xSeyS1-y /CdzZn1-zPreparation of S
Preparing cadmium oleate and zinc oleate precursors:0.4 mmol of cadmium oxide (CdO), 8 mmol of zinc acetate [ Zn (acet) ]2]10mL of Oleic acid (Oleic acid) was placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
Dissolving 2mmol Selenium powder (Selenium powder) and 4 mmol Sulfur powder (Sulfur powder) in 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
2mmol of Sulfur powder (Sulfur powder) was dissolved in 2mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, quickly injecting trioctylphosphine selenide-trioctylphosphine sulfide precursors into a reaction system, and rapidly injecting Cd into the reaction systemxZn1-xSeyS1-yAnd (3) quickly nucleating, reacting for 10 min, and then dropwise adding 2mL of trioctylphosphine sulfide precursor into the reaction system at the speed of 8 mL/h until the precursor is injected completely. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using methylbenzene and absolute methanol, and centrifugally purifying to obtain the green quantum dot Cd with the funnel-type energy level structure with the opening gradually enlargedxZn1-xSeyS1-y /CdzZn1-zS; as shown in FIG. 9, the peak wavelength of the emission was 542nm, and the absorbance gradually decreased with the increase in the wavelength.
Example 12: red quantum dot Cd with specific structure 1xZn1-xSeyS1-y/CdzZn1-zPreparation of S
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet)2], 14 mL of Oleic acid (Oleic acid) were placed in a 100 mL three-necked flask and degassed under vacuum at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol Selenium powder (Selenium powder) is added into 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
Dissolving 0.2mmol Selenium powder (Selenium powder) and 0.6 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting trioctylphosphine selenide precursors into a reaction system, and adding Cd into the reaction systemxZn1-xSe nucleates rapidly, and after the reaction is carried out for 10 min, 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor is added into the reaction system drop by drop at the speed of 4 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using methylbenzene and absolute methanol, and centrifugally purifying to obtain the Cd with the funnel-type energy level structure with the opening gradually enlargedxZn1-xSeyS1-y/CdzZn1-zS red fluorescent quantum dots; as shown in FIG. 10, the peak wavelength of the emission was 631nm, and the absorbance gradually decreased with the increase in the wavelength. .
Example 13: effect of cadmium oleate injection Rate on the Synthesis of blue Quantum dots with specific Structure 1
On the basis of the embodiment 10, the gradient change slope of the components of the quantum dots can be regulated and controlled by regulating the injection rate of the cadmium oleate, so that the change of the funnel-shaped energy level structure of the quantum dots is influenced, and the regulation and control of the wavelength of the quantum dots are finally realized.
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet)2], 8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the precursor into a reaction system, and quickly injecting CdxZn1-xS is rapidly nucleated, after the reaction is carried out for 10 min, 3mL of trioctylphosphine sulfide precursor is dropwise added into the reaction system at the rate of 3 mL/h, and meanwhile, the cadmium oleate precursor is dropwise added into the reaction system at different injection rates. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the blue fluorescent Cd with the funnel-type energy level structure with the gradually-enlarged openingxZn1-xS/CdyZn1-yAnd (4) S quantum dots.
Based on the same core (alloy quantum dot emission peak 447 nm) and the wavelength of the alloy quantum dot emission at the injection rate of different cadmium oleate precursors, the list of adjusting the injection rate of the cadmium oleate precursor to realize the wavelength adjustment of the quantum dot emission is as follows:
cadmium oleate injection rate (mmol/h) Luminous wavelength (nm)
0.5 449
0.75 451
1 453
1.25 455
1.5 456
Example 14: effect of cadmium oleate injection on the Synthesis of blue Quantum dots with specific Structure 1
On the basis of the embodiment 10 and the embodiment 13, the gradient change interval of the components of the quantum dots can be regulated and controlled by regulating the injection amount of the cadmium oleate, so that the change of the funnel-shaped energy level structure of the quantum dots is influenced, and the regulation and control of the wavelength of the quantum dots are finally realized. Based on the wavelength of the quantum dot light of the alloy under the speed of the same core (the luminous peak of the quantum dot of the alloy 447 nm) and the injection amount (1 mmol/h under the same injection speed) of different cadmium oleate precursors, the following table is provided:
cadmium oleate injection amount (mmol) Luminous wavelength (nm)
0.4 449
0.5 451
0.6 453
0.8 454
1.0 455
Example 15: preparation of blue Quantum dots with specific Structure 2
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid) and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generating CdxZn1-xAnd S, after reacting for 10 min, reducing the temperature of the reaction system to 280 ℃, and then simultaneously injecting 2mL of trioctylphosphine sulfide precursor and 6mL of cadmium oleate precursor into the reaction system at the speed of 3 mL/h and 10mL/h respectively. And after the injection is carried out for 40 min, heating the temperature of the reaction system to 310 ℃, injecting 1mL of trioctylphosphine sulfide precursor into the reaction system at the speed of 3 mL/h, after the reaction is finished, cooling the reaction liquid to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and carrying out centrifugal purification to obtain the blue quantum dot with the quantum well energy level structure.
Example 16: preparation of Green Quantum dots with specific Structure 2
Preparing cadmium oleate and zinc oleate precursors: 0.4 mmol of cadmium oxide (CdO), 8 mmol of zinc acetate [ Zn (acet)2], 10mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
Dissolving 2mmol Selenium powder (Selenium powder) and 4 mmol Sulfur powder (Sulfur powder) in 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
2mmol of Sulfur powder (Sulfur powder) was dissolved in 2mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, quickly injecting trioctylphosphine selenide-trioctylphosphine sulfide precursors into a reaction system, and firstly generating CdxZn1-xSeyS1-yAfter reacting for 10 min, reducing the temperature of the reaction system to 280 ℃, and then injecting 1.2mL of trioctylphosphine sulfide precursor and 6mL of cadmium oleate precursor into the reaction system at the speed of 2 mL/h and 10mL/h respectively until the precursors are completely injected. The temperature of the reaction system is increased to 310 ℃, and 0.8 mL of trioctylphosphine sulfide precursor is injected into the reaction system at the speed of 2 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the green quantum dot with the quantum well energy level structure.
Example 17: preparation of Red Quantum dots having specific Structure 2
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet) ]2]14 mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. Then will beIt was switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol Selenium powder (Selenium powder) is added into 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
Dissolving 0.2mmol Selenium powder (Selenium powder) and 0.6 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Placing 0.3 mmol of cadmium oxide (CdO), 0.3mL of Oleic acid (Oleic acid) and 2.7 mL of Octadecene (1-octaecene) in a 50 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting trioctylphosphine selenide precursors into a reaction system, and firstly generating CdxZn1-xSe, after reacting for 10 min, reducing the temperature of the reaction system to 280 ℃, and then injecting 1mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor and 3mL of cadmium oleate precursor into the reaction system at the speed of 2 mL/h and 6 mL/h respectively. The temperature of the reaction system is increased to 310 ℃, and 1mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor is injected into the reaction system at the speed of 4 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the red quantum dot with the quantum well energy level structure.
Example 18: preparation of blue Quantum dots with specific Structure 3
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
0.2mmol of Selenium powder (Selenium powder) is dissolved in 1mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine selenide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generating CdxZn1-xS is rapidly nucleated, and after the reaction is carried out for 10 min, the cadmium oleate precursor and the trioctylphosphine sulfide precursor are continuously injected into the reaction system for 20 min at the speed of 0.6 mmol/h and 4 mmol/h respectively. And then continuously injecting the cadmium oleate precursor, the trioctylphosphine sulfide precursor and the trioctylphosphine selenide precursor into the reaction system for 1 hour at the speed of 0.4 mmol/h, 0.6 mmol/h and 0.2 mmol/h respectively. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and absolute methanol, and centrifugally purifying to obtain the blue quantum dots (CdZnS/CdZnS/CdZnSeS) with the quantum well energy level structure3)。
Example 19: preparation of Green Quantum dots with specific Structure 3
Preparing cadmium oleate and zinc oleate precursors: 0.4 mmol of cadmium oxide (CdO), 6mmol of zinc acetate [ Zn (acet) ]2]10mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
0.4 mmol of Selenium powder (Selenium powder) and 4 mmol of Sulfur powder (Sulfur powder) are dissolved in 4mL of Trioctylphosphine (Trioctylphosphine), and a precursor 1 of Trioctylphosphine selenide-Trioctylphosphine sulfide is obtained.
Dissolving 0.1 mmol Selenium powder (Selenium powder) and 0.3 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor 2 of Trioctylphosphine selenide-Trioctylphosphine sulfide.
0.8 mmol of Sulfur powder (Sulfur powder) and 0.8 mmol of Selenium powder (Selenium powder) are dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine selenide-Trioctylphosphine sulfide precursor 3.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, quickly injecting trioctylphosphine selenide-trioctylphosphine sulfide precursor 1 into a reaction system, and firstly generating CdxZn1-xSeyS1-yAfter 5min of reaction, 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor 2 was added dropwise to the reaction system at a rate of 6 mL/h. Subsequently, 3mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor 3 and 6mL of cadmium oleate precursor were continuously added dropwise to the reaction system at 3 mL/h and 6 mL/h rates, respectively. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the green quantum dot (CdZn) with the quantum well energy level structure3SeS3/Zn4SeS3/Cd3Zn5Se4S4)。
Example 20: preparation of Red Quantum dots having specific Structure 3
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet) ]2]14 mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol Selenium powder (Selenium powder) is added into 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
Dissolving 0.2mmol Selenium powder (Selenium powder) and 0.6 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Placing 0.9 mmol of cadmium oxide (CdO), 0.9 mL of Oleic acid (Oleic acid) and 8.1 mL of Octadecene (1-Octadecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting trioctylphosphine selenide precursors into a reaction system, and firstly generating CdxZn1-xSe, after reacting for 10 min, dropwise adding 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor into the reaction system at the speed of 2 mL/h. When the solution is injected for 30 min, 3mL of cadmium oleate precursor is added dropwise into the reaction system at the rate of 6 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the red quantum dot (Cd) with the quantum well energy level structurexZn1-xSe/ZnSeyS1-y/CdzZn1-zSeS）。
Example 21: preparation of blue Quantum dots with specific Structure 4
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
0.2mmol of Selenium powder (Selenium powder) is dissolved in 1mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine selenide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generating CdxZn1-xAnd S, after reacting for 10 min, continuously injecting the cadmium oleate precursor and the trioctylphosphine selenide precursor into the reaction system at the speed of 0.6 mmol/h and the speed of 0.6 mmol/h for 20 min respectively. And then continuously injecting the cadmium oleate precursor and the trioctylphosphine sulfide precursor into the reaction system for 1 hour at the speed of 0.4 mmol/h and 6mmol/h respectively. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and absolute methanol, and centrifugally purifying to obtain the blue quantum dot (CdZnS/CdZnSe/CdZnS) with the quantum well energy level structure.
Example 22: preparation of Green Quantum dots with specific Structure 4
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
0.4 mmol of Selenium powder (Selenium powder) is dissolved in 2mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine selenide precursor.
Placing 0.8 mmol of cadmium oxide (CdO), 1.2mL of Oleic acid (Oleic acid) and 4.8 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generating CdxZn1-xAnd S, after reacting for 10 min, continuously injecting the cadmium oleate precursor and the trioctylphosphine selenide precursor into the reaction system for 40 min at the speed of 0.6 mmol/h and 0.6 mmol/h respectively. And then continuously injecting the cadmium oleate precursor and the trioctylphosphine sulfide precursor into the reaction system for 1 hour at the speed of 0.4 mmol/h and 6mmol/h respectively. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and absolute methanol, and centrifugally purifying to obtain the green quantum dot (CdZnS/CdZnSe/CdZnS) with the quantum well energy level structure.
Example 23: preparation of Red Quantum dots having specific Structure 4
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet) ]2]14 mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
Dissolving 1.5 mmol Selenium powder (Selenium powder) and 1.75 mmol Sulfur powder (Sulfur powder) in 3mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor 1 of Trioctylphosphine selenide-Trioctylphosphine sulfide.
1 mmol Selenium powder (Selenium powder) is added into 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
Dissolving 0.2mmol Selenium powder (Selenium powder) and 0.8 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor 2 of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Placing 3 mmol of cadmium oxide (CdO), 3mL of Oleic acid (Oleic acid) and 6mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, injecting trioctylphosphine selenide-trioctylphosphine sulfide precursor 1 into a reaction system, and firstly generating CdxZn1-xSe, after reacting for 10 min, dropwise adding 2mL of trioctylphosphine selenide precursor and 3mL of cadmium oleate precursor into the reaction system at the rates of 4 mL/h and 6 mL/h respectively. When the solution is injected for 30 min, 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor 2 and 3mL of cadmium oleate precursor are respectively added into the reaction system drop by drop at the speed of 2 mL/h and 3 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the red quantum dot (Cd) with the quantum well energy level structurexZn1- xSe/CdZnSe/CdzZn1-zSeS）。
Example 24: preparation of blue Quantum dots with specific Structure 5
Preparing cadmium oleate and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
1 mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a precursor of the thiaoctadecene.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generatingCdxZn1-xS, after reacting for 10 min, continuously injecting 3mL of trioctylphosphine sulfide precursor into the reaction system at the rate of 3 mL/h for 1h, injecting 2mL of cadmium oleate precursor into the reaction system at the rate of 6 mL/h when the trioctylphosphine sulfide precursor is injected for 20 min, and injecting 4mL of cadmium oleate precursor into the reaction system at the rate of 12 mL/h when the trioctylphosphine sulfide precursor is injected for 40 min. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and absolute methanol, and centrifugally purifying to obtain the blue quantum dot (CdZnS/ZnS/CdZnS) with the quantum well energy level structure.
Example 25: preparation of Green Quantum dots with specific Structure 5
Preparing cadmium oleate and zinc oleate precursors: 0.4 mmol of cadmium oxide (CdO), 6mmol of zinc acetate [ Zn (acet) ]2]10mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
0.4 mmol of Selenium powder (Selenium powder) and 4 mmol of Sulfur powder (Sulfur powder) are dissolved in 4mL of Trioctylphosphine (Trioctylphosphine), and a precursor 1 of Trioctylphosphine selenide-Trioctylphosphine sulfide is obtained.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, quickly injecting trioctylphosphine selenide-trioctylphosphine sulfide precursors into a reaction system, and firstly generating CdxZn1-xSeyS1-yAfter reacting for 10 min, 3mL of trioctylphosphine sulfide precursor is continuously injected into the reaction system for 1h at the rate of 3 mL/h, and when the trioctylphosphine sulfide precursor is injected for 20 min, the reaction system is used for continuously injecting the trioctylphosphine sulfide precursor into the reaction system for 1h2mL of cadmium oleate precursor is injected into the reaction system at a rate of 6 mL/h, and 4mL of cadmium oleate precursor is injected into the reaction system at a rate of 12 mL/h when trioctylphosphine sulfide precursor is injected for 40 min. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and absolute methanol, and centrifugally purifying to obtain the green quantum dot (CdZnSeS/ZnS/CdZnS) with the quantum well energy level structure.
Example 26: preparation of Red Quantum dots having specific Structure 5
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet) ]2]14 mL of Oleic acid (Oleic acid) and 20 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol Selenium powder (Selenium powder) is added into 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting trioctylphosphine selenide precursors into a reaction system, and firstly generating CdxZn1-xSe, after reacting for 10 min, continuously injecting trioctylphosphine sulfide precursor into the reaction system for 1h at the speed of 6mmol/h, injecting 0.2mmol of cadmium oleate precursor into the reaction system at the speed of 0.6 mmol/h when S-TOP is injected for 20 min, and injecting 0.4 mmol of cadmium oleate precursor into the reaction system at the speed of 1.2 mmol/h when S-TOP is injected for 40 min. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using methylbenzene and absolute methanol, and centrifugally purifying to obtain the product with the quantum well energy level structureRed quantum dots (CdZnSe/ZnS/CdZnS).
Example 27: preparation of blue Quantum dots with specific Structure 6
Preparing acid cadmium and zinc oleate precursors: 1 mmol of cadmium oxide (CdO), 9 mmol of zinc acetate [ Zn (acet) ]2]8 mL of Oleic acid (Oleic acid), and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 min under the atmosphere of nitrogen to obtain a transparent cadmium oleate precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in a nitrogen atmosphere, quickly injecting the thiooctadecene precursors into a reaction system, and firstly generating CdxZn1-xAnd S, after reacting for 10 min, dropwise adding the trioctylphosphine sulfide precursor and the cadmium oleate precursor into the reaction system at the speed of 6mmol/h and 0.6 mmol/h respectively. After 30 min, the temperature of the reaction system is reduced to 280 ℃, and the residual trioctylphosphine sulfide precursor and cadmium oleate precursor are respectively added into the reaction system drop by drop at the speed of 6mmol/h and 0.6 mmol/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the blue quantum dot (Cd) with the specific structure 6xZn1-xS）。
Example 28: preparation of Green Quantum dots with specific Structure 6
Preparing cadmium oleate and zinc oleate precursors: 0.4 mmol of cadmium oxide (CdO), 8 mmol of zinc acetate [ Zn (acet) ]2]10mL Oleic acid (Oleic acid)Placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
Dissolving 2mmol Selenium powder (Selenium powder) and 4 mmol Sulfur powder (Sulfur powder) in 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
2mmol of Sulfur powder (Sulfur powder) was dissolved in 2mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Heating cadmium oleate and zinc oleate precursors to 310 ℃ in the nitrogen atmosphere, quickly injecting trioctylphosphine selenide-trioctylphosphine sulfide precursors into a reaction system, and firstly generating CdxZn1-xSeyS1-yAnd after the reaction is carried out for 10 min, the temperature of the reaction system is reduced to 280 ℃, and the trioctylphosphine sulfide precursor is dropwise added into the reaction system at the speed of 4 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the green quantum dot (Cd) with the specific structure 6xZn1-xSeyS1-y/ZnS）。
Example 29: preparation of Red Quantum dots with specific Structure 6
Preparing cadmium oleate and zinc oleate precursors: 0.8 mmol of cadmium oxide (CdO), 12 mmol of zinc acetate [ Zn (acet) ]2]14 mL of Oleic acid (Oleic acid) was placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 min. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
2mmol Selenium powder (Selenium powder) is added into 4mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide.
Dissolving 0.2mmol Selenium powder (Selenium powder) and 0.6 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Heating cadmium oleate and zinc oleate precursors in a nitrogen atmosphereAt 310 ℃, rapidly injecting trioctylphosphine selenide precursor into a reaction system, and CdxZn1-xSe fast nucleates, after reaction for 10 min, the temperature of a reaction system is reduced to 280 ℃, and the trioctylphosphine selenide-trioctylphosphine sulfide precursor is dropwise added into the reaction system at the speed of 4 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the red quantum dot (Cd) with the specific structure 6xZn1-xSe/ZnSeS）。
Example 30: preparation of blue Quantum dots with specific Structure 7
Preparing a first precursor of cadmium oleate: 1 mmol of cadmium oxide (CdO), 1mL of Oleic acid (Oleic acid) and 5 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 mins. It was then switched to a nitrogen atmosphere and stored at this temperature for future use.
Preparing a cadmium oleate second precursor: placing 0.6 mmol of cadmium oxide (CdO), 0.6mL of Oleic acid (Oleic acid) and 5.4 mL of Octadecene (1-octaecene) in a 100 mL three-neck flask, and heating and refluxing at 250 ℃ for 120 mins under the atmosphere of nitrogen to obtain a transparent cadmium oleate second precursor.
Preparing a zinc oleate precursor: 9 mmol of zinc acetate [ Zn (acet)2], 7 mL of Oleic acid (Oleic acid), and 10mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask, and vacuum-degassed at 80 ℃ for 60 mins. Then, the nitrogen atmosphere is switched to be used, and the heating reflux is carried out at 250 ℃ under the nitrogen atmosphere for storage so as to be ready for use.
2mmol of Sulfur powder (sulfurer powder) is dissolved in 3mL of Octadecene (1-Octadecene) to obtain a thiooctadecene precursor.
6mmol of Sulfur powder (Sulfur powder) was dissolved in 3mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine sulfide precursor.
Heating a cadmium oleate first precursor to 310 ℃ in a nitrogen atmosphere, quickly injecting a sulfur octadecene precursor into a reaction system to quickly generate CdS, after reacting for 10 mins, completely injecting a zinc oleate precursor into the reaction system, and then simultaneously injecting 3mL of trioctylphosphine sulfide precursor and 6mL of cadmium oleate second precursor into the reaction system at the speed of 3 mL/h and 10mL/h respectively.
After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using toluene and anhydrous methanol, and centrifugally purifying to obtain the blue quantum dot with the quantum well energy level structure.
Example 31: preparation of Green Quantum dots with specific Structure 7
Preparing a cadmium oleate precursor: 0.4 mmol of cadmium oxide (CdO), 1mL of Oleic acid (Oleic acid) and 5 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 mins. It was then heated to reflux at 250 ℃ under nitrogen and stored at this temperature for use.
0.4 mmol Selenium powder (Selenium powder) was dissolved in 4mL Trioctylphosphine (Trioctylphosphine) to obtain Trioctylphosphine selenide.
Preparing a zinc oleate precursor: 8 mmol of zinc acetate [ Zn (acet) ]2]9 mL of Oleic acid (Oleic acid) and 15 mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 mins. And heating and refluxing for 120 mins at 250 ℃ in the nitrogen atmosphere to obtain a transparent zinc oleate precursor.
2mmol of Sulfur powder (Sulfur powder) and 1.6 mmol of Selenium powder (Selenium powder) are dissolved in 2mL of Trioctylphosphine (Trioctylphosphine), and a Trioctylphosphine selenide-Trioctylphosphine sulfide precursor is obtained.
Heating a cadmium oleate precursor to 310 ℃ in a nitrogen atmosphere, quickly injecting a trioctylphosphine selenide precursor into a reaction system to quickly generate CdSe, reacting for 5 mins, completely injecting a zinc oleate precursor into the reaction system, and dropwise adding 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor into the reaction system at a rate of 2 mL/h until the precursor is completely injected. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using methylbenzene and absolute methanol, and centrifugally purifying to obtain the green fluorescent quantum dot with the quantum well energy level structure.
Example 32: preparation of Red Quantum dots having specific Structure 7
Preparing a cadmium oleate precursor: 0.8 mmol of cadmium oxide (CdO), 4mL of Oleic acid (Oleic acid) and 10mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 mins. It was then heated to reflux at 250 ℃ under nitrogen and stored at this temperature for use.
Preparing a zinc oleate precursor: 12 mmol of Zinc acetate [ Zn (acet)2]10mL of Oleic acid (Oleic acid) and 10mL of Octadecene (1-Octadecene) were placed in a 100 mL three-necked flask and vacuum degassed at 80 ℃ for 60 mins.
0.8 mmol of Selenium powder (Selenium powder) is added into 4mL of Trioctylphosphine (Trioctylphosphine) to obtain a Trioctylphosphine selenide precursor.
Dissolving 1 mmol Selenium powder (Selenium powder) and 0.6 mmol Sulfur powder (Sulfur powder) in 2mL Trioctylphosphine (Trioctylphosphine) to obtain the precursor of Trioctylphosphine selenide-Trioctylphosphine sulfide.
Heating a cadmium oleate precursor to 310 ℃ in a nitrogen atmosphere, quickly injecting a trioctylphosphine selenide precursor into a reaction system to quickly generate CdSe, reacting for 10 mins, completely injecting a zinc oleate precursor into the reaction system, and dropwise adding 2mL of trioctylphosphine selenide-trioctylphosphine sulfide precursor into the reaction system at a rate of 4 mL/h. After the reaction is finished, after the reaction liquid is cooled to room temperature, repeatedly dissolving and precipitating the product by using methylbenzene and absolute methanol, and centrifugally purifying to obtain the red fluorescent quantum dot with the quantum well energy level structure.
Example 33
The quantum dot light emitting diode of the present embodiment, as shown in fig. 11, sequentially includes from bottom to top: ITO substrate 11, bottom electrode 12, PEDOT: PSS hole injection layer 13, poly-TPD hole transport layer 14, quantum dot light emitting layer 15, ZnO electron transport layer 16 and Al top electrode 17.
The preparation steps of the quantum dot light-emitting diode are as follows:
a bottom electrode 12, a 30 nm PEDOT: after the PSS hole injection layer 13 and the 30 nm poly-TPD hole transport layer 14, a quantum dot light emitting layer 15 with the thickness of 20 nm is prepared on the poly-TPD hole transport layer 14, and then a 40 nm ZnO electron transport layer 16 and a 100 nm Al top electrode 17 are prepared on the quantum dot light emitting layer 15. The nanocomposite of the quantum dot light emitting layer 15 is the nanocomposite as described in example 10.
Example 34
In this embodiment, as shown in fig. 12, the quantum dot light emitting diode sequentially includes, from bottom to top: ITO substrate 21, bottom electrode 22, PEDOT: PSS hole injection layer 23, Poly (9-vinylcarbazole) (PVK) hole transport layer 24, quantum dot light emitting layer 25, ZnO electron transport layer 26 and Al top electrode 27.
The preparation steps of the quantum dot light-emitting diode are as follows:
a bottom electrode 22, a 30 nm PEDOT: after the PSS hole injection layer 23 and the 30 nm PVK hole transport layer 24, a quantum dot light emitting layer 25 with the thickness of 20 nm is prepared on the PVK hole transport layer 24, and then a 40 nm ZnO electron transport layer 26 and a 100 nm Al top electrode 27 are prepared on the quantum dot light emitting layer 25. The nanocomposite of the quantum dot light emitting layer 25 is the nanocomposite as described in example 15.
Example 35
The quantum dot light emitting diode of the present embodiment, as shown in fig. 13, sequentially includes from bottom to top: ITO substrate 31, bottom electrode 32, PEDOT: PSS hole injection layer 33, poly-TPD hole transport layer 34, quantum dot light emitting layer 35, TPBi electron transport layer 36, and Al top electrode 37.
The preparation steps of the quantum dot light-emitting diode are as follows:
a bottom electrode 32, a 30 nm PEDOT: after the PSS hole injection layer 33 and the 30 nm poly-TPD hole transport layer 34, a quantum dot light emitting layer 35 with the thickness of 20 nm is prepared on the poly-TPD hole transport layer 34, and then a 30 nm TPBi electron transport layer 36 and a 100 nm Al top electrode 37 are prepared on the quantum dot light emitting layer 35 through a vacuum evaporation method. The nanocomposite of the quantum dot light emitting layer 35 is the nanocomposite as described in example 18.
Example 36
The quantum dot light emitting diode of the present embodiment, as shown in fig. 14, sequentially includes from bottom to top: ITO substrate 41, bottom electrode 42, ZnO electron transport layer 43, quantum dot light emitting layer 44, NPB hole transport layer 45, MoO3A hole injection layer 46 and an Al top electrode 47.
The preparation steps of the quantum dot light-emitting diode are as follows:
sequentially preparing a bottom electrode 42 and a 40 nm ZnO electron transmission layer 43 on an ITO substrate 41, preparing a quantum dot light emitting layer 44 with the thickness of 20 nm on the ZnO electron transmission layer 43, and then preparing a 30 nm NPB hole transmission layer 45 and a5 nm MoO through a vacuum evaporation method3A hole injection layer 46 and a 100 nm Al top electrode 47. The nanocomposite of the quantum dot light emitting layer 44 is a nanocomposite as described in example 21.
Example 37
The quantum dot light emitting diode of the present embodiment, as shown in fig. 15, sequentially includes from bottom to top: glass substrate 51, Al electrode 52, PEDOT: PSS hole injection layer 53, poly-TPD hole transport layer 54, quantum dot light emitting layer 55, ZnO electron transport layer 56, and ITO top electrode 57.
The preparation steps of the quantum dot light-emitting diode are as follows:
a 100 nm Al electrode 52 was prepared on a glass substrate 51 by a vacuum evaporation method, and then 30 nm PEDOT: after the PSS hole injection layer 53 and the 30 nm poly-TPD hole transport layer 54, a quantum dot light emitting layer 55 is prepared on the poly-TPD hole transport layer 54, the thickness is 20 nm, then a 40 nm ZnO electron transport layer 56 is prepared on the quantum dot light emitting layer 55, and finally 120 nm ITO is prepared through a sputtering method to serve as a top electrode 57. The nanocomposite of the quantum dot light emitting layer 55 is the nanocomposite as described in example 24.
Example 38
As shown in fig. 16, the quantum dot light emitting diode of this embodiment includes, in order from bottom to top: a glass substrate 61, an Al electrode 62, a ZnO electron transport layer 63, a quantum dot light emitting layer 64, an NPB hole transport layer 65, MoO3A hole injection layer 66 and an ITO top electrode 67.
The preparation steps of the quantum dot light-emitting diode are as follows:
preparing a 100 nm Al electrode 62 on a glass substrate 61 by a vacuum evaporation method, then sequentially preparing a 40 nm ZnO electron transport layer 63 and a 20 nm quantum dot light emitting layer 64, and then preparing a 30 nm NPB hole transport layer 65 and a5 nm MoO by the vacuum evaporation method3A hole injection layer 66 and finally 120 nm ITO as a top electrode 67 were prepared by a sputtering method. The nanocomposite of the quantum dot light emitting layer was the nanocomposite as described in example 27.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (14)

1. A method of preparing a nanocomposite, comprising the steps of:
adding more than one kind of cation precursor at a preset position in the radial direction; adding more than one anion precursor simultaneously under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position;
wherein the content of the first and second substances,
the molar charge ratio of the cation precursor to the anion precursor is between 100:1 and 1: 50;
the wavelength of the luminescence peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, and the method specifically comprises the following steps:
the wavelength of the luminescence peak of the nano composite material generates continuous blue shift in the reaction process; alternatively, the first and second electrodes may be,
the wavelength of the luminescence peak of the nano composite material is alternately blue-shifted and unchanged in the reaction process; alternatively, the first and second electrodes may be,
the wavelength of the luminescence peak of the nano composite material has alternate blue shift and red shift in the reaction process; alternatively, the first and second electrodes may be,
the wavelength of the luminescence peak of the nano composite material appears discontinuous blue shift in the reaction process; alternatively, the first and second electrodes may be,
the wavelength of the luminescence peak of the nano composite material is discontinuously red-shifted in the reaction process; alternatively, the first and second electrodes may be,
the wavelength of the luminous peak of the nano composite material firstly appears blue shift in the reaction process and then does not change; alternatively, the first and second electrodes may be,
the wavelength of the luminescence peak of the nano composite material is continuously red shifted in the reaction process;
the cation precursor and the anion precursor with high reactivity react firstly to form a first compound, the cation precursor and the anion precursor with low reactivity react later to form a second compound, and in the reaction process, cation exchange reaction occurs between the two compounds formed by successive reaction, so that the distribution of the alloy components is realized;
the cation precursor comprises a precursor of Zn and a precursor of Cd;
the anion precursor includes at least one of a precursor of Se, a precursor of S, and a precursor of Te.
2. The method for preparing a nanocomposite as claimed in claim 1, wherein a cation precursor is added at a predetermined position in a radial direction; under a certain condition, two anion precursors with different reaction activities are simultaneously added, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
3. The method for preparing a nanocomposite as claimed in claim 1, wherein two kinds of cation precursors having different reactivity are added at predetermined positions in a radial direction; and simultaneously adding an anion precursor under a certain condition, so that the cation precursor and the anion precursor react to form the nano composite material, and the wavelength of the luminous peak of the nano composite material is subjected to one or more of blue shift, red shift and invariance in the reaction process, thereby realizing the distribution of the alloy components at the preset position.
4. The method of claim 1, wherein the Zn precursor is at least one of dimethyl zinc, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, or zinc sulfate.
5. The method for preparing the nanocomposite material as claimed in claim 1, wherein the precursor of Cd is at least one of cadmium dimethyl, cadmium diethyl, cadmium acetate, cadmium acetylacetonate, cadmium iodide, cadmium bromide, cadmium chloride, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate, or cadmium sulfate.
6. The method of claim 1, wherein the one or more anionic precursors are added simultaneously under heating.
7. The method of claim 6, wherein the precursor of Se is at least one of Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
8. The method of claim 6, wherein the precursor of S is at least one of S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl thiol.
9. The method of claim 6, wherein the precursor of Te is at least one of Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
10. The method of claim 6, wherein the heating temperature is between 100 ℃ and 400 ℃.
11. Process for the preparation of a nanocomposite according to claim 6, characterized in that the heating time is between 2s and 24 h.
12. A nanocomposite material, characterized in that the nanocomposite material is prepared by the preparation method according to any one of claims 1 to 11.
13. A semiconductor device comprising the nanocomposite material of claim 12.
14. The semiconductor device according to claim 13, wherein the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a solar cell, a display device, a photodetector, a biological probe, and a nonlinear optical device.
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