CN113122232A - Quantum dot material, preparation method thereof and quantum dot light-emitting diode - Google Patents
Quantum dot material, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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- CN113122232A CN113122232A CN201911419489.5A CN201911419489A CN113122232A CN 113122232 A CN113122232 A CN 113122232A CN 201911419489 A CN201911419489 A CN 201911419489A CN 113122232 A CN113122232 A CN 113122232A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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Abstract
The invention provides a preparation method of a quantum dot material, which comprises the following steps: preparing a precursor solution containing zinc, cadmium and sulfur, and heating the precursor solution to a first reaction temperature in an inert atmosphere to obtain Cd1‑xZnxS quantum dot core solution; under inert atmosphere at a second reaction temperature, under the action of the carrier gas, and in the presence of the Cd1‑xZnxAdding a first sulfur precursor, a first cadmium precursor and a first zinc precursor into the S quantum dot core solution, and carrying out a first shell reaction to obtain Cd1‑xZnxS/Cd1‑yZnyS quantum dot solution; under inert atmosphere at a third reaction temperature in the presence of Cd1‑ xZnxS/Cd1‑yZnyAdding a second sulfur precursor, a second cadmium precursor and a second zinc precursor into the S quantum dot solutionCarrying out shell layer reaction to prepare Cd1‑xZnxS/Cd1‑yZnyS/Cd1‑zZnzAnd (4) S quantum dots.
Description
Technical Field
The invention belongs to the technical field of quantum dot materials, and particularly relates to a quantum dot material and a preparation method thereof, a quantum dot light-emitting diode and a light-emitting device.
Background
Quantum Dots (QDs), also called semiconductor nanocrystals, have the advantages of strong fluorescence emission, high quantum yield, narrow half-peak width, continuously adjustable size and light-emitting wavelength and the like, and the excellent optical properties enable the quantum dots to have wide application prospects in the fields of photoelectric devices, biological imaging, fluorescent labeling and the like. In recent years, the display industry has been rapidly developed, the competition of panel enterprises is more intense, and after the traditional LCD panel technology and profit reach a certain bottleneck, the demand and development of novel display materials and display technologies are urgent. Light Emitting Diode (QLED) devices based on quantum dots have attracted attention from well-known display companies including samsung, TCL, etc. due to their advantages of high color purity, wide color gamut, etc.
Over thirty years of research and development, the synthesis method of the quantum dot tends to mature. Quantum dot films based on high-quality red and green quantum dots and quantum dot electroluminescent devices (QLEDs) are developed rapidly and basically meet industrial requirements. However, the instability of blue quantum dots, especially for QLEDs based on blue quantum dots, has not met the needs of the industry due to lifetime issues. The service life of the blue light QLED device is mainly caused by the fact that the energy level of the blue quantum dots is poor in energy level matching degree with the energy level of the hole transmission material, the lattice adaptation between the nuclear shell of the nuclear shell quantum dots is large, and the like. Therefore, how to prepare the quantum dots with high fluorescence quantum yield, reasonable core-shell structure and energy level matching with the hole transport material becomes the key for solving the problem.
Disclosure of Invention
The invention aims to provide a quantum dot material and a preparation method thereof, a quantum dot light-emitting diode containing the quantum dot material and a light-emitting device containing the quantum dot light-emitting diode, and aims to solve the problems that the energy level of the existing quantum dot, particularly blue quantum dot, is poor in energy level matching degree with a hole transport material, and the lattice adaptation between the nuclear shell and the nuclear shell of the nuclear shell quantum dot is large.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a quantum dot material, which comprises the following steps:
preparing a precursor solution containing zinc, cadmium and sulfur, and heating the precursor solution to a first reaction temperature in an inert atmosphere to obtain Cd1- xZnxS quantum dot core solution;
in a second reaction under an inert atmosphereAt a temperature of said Cd1-xZnxAdding a first sulfur precursor, a first cadmium precursor and a first zinc precursor into the S quantum dot core solution, carrying out a first shell layer reaction, and adding Cd into the solution1-xZnxSurface growth Cd of S quantum dot core1-yZnyS shell layer to obtain Cd1-xZnxS/Cd1-yZnyS quantum dot solution;
under inert atmosphere at a third reaction temperature in the presence of Cd1-xZnxS/Cd1-yZnyAdding a second sulfur precursor, a second cadmium precursor and a second zinc precursor into the S quantum dot solution, and carrying out shell layer reaction on the S quantum dot solution, wherein Cd is1-xZnxS/Cd1-yZnySurface growth Cd of S quantum dot1-zZnzS shell layer, preparing Cd1-xZnxS/Cd1-yZnyS/Cd1-zZnzS quantum dots;
wherein, the value ranges of x, y and z satisfy: x is more than or equal to 0 and less than y and z is less than or equal to 1.
A second aspect of the invention provides a quantum dot material, the blue quantum dot material comprising Cd1-xZnxS quantum dot core of Cd1-xZnxCd formed on surface of S quantum dot core1-yZnyS shell layer, and Cd1-yZnyCd formed on surface of S shell1-zZnzAnd (2) an S shell layer, wherein the value ranges of x, y and z meet the following requirements: x is more than or equal to 0<y<z≤1。
The invention provides a quantum dot light-emitting diode, which comprises an anode and a cathode which are oppositely arranged, and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein the material of the quantum dot light-emitting layer comprises the quantum dot material, or the material of the quantum dot light-emitting layer comprises the quantum dot material prepared by the method.
The invention provides a light-emitting device, which comprises a quantum dot light-emitting diode, wherein the quantum dot light-emitting diode is the quantum dot light-emitting diode.
The invention provides a preparation method of quantum dot material,preparing shell layers formed by Cd, Zn and S elements layer by layer, and regulating the addition amount of a cadmium precursor solution and a zinc precursor solution in the shell layer preparation process to obtain the core-shell structure quantum dot with continuously gradually changed Cd and Zn. Cd prepared by the method1-xZnxS/Cd1-yZnyS/Cd1-zZnzIn the S quantum dots, the Zn content is higher and higher from inside to outside. The core-shell quantum dot with the structure has wider forbidden band width of a shell material, effectively confines electrons and holes in a core, and improves the fluorescence quantum yield of the quantum dot; in the shell structure, the energy level is gradually changed along with the increase of the forbidden bandwidth of the materials from inside to outside along with the proportion of zinc, and the final energy level of the quantum dots can be adjusted by simply adjusting the components of the shell, so that the quantum dots are effectively matched and adapted to hole transport materials with different energy levels. In conclusion, the preparation method of the quantum dot material provided by the invention can prepare the quantum dot which has high fluorescence quantum yield, reasonable core-shell structure and energy level matching with the hole transport material, thereby promoting the development of blue light quantum dot light-emitting diode devices.
The quantum dot material provided by the invention has higher and higher Zn content from inside to outside. The core-shell quantum dot with the structure has wider forbidden band width of a shell material, effectively confines electrons and holes in a core, and improves the fluorescence quantum yield of the quantum dot; in the shell structure, the energy level is gradually changed along with the increase of the forbidden bandwidth of the materials from inside to outside along with the proportion of zinc, and the final energy level of the quantum dots can be adjusted by simply adjusting the components of the shell, so that the quantum dots are effectively matched and adapted to hole transport materials with different energy levels. Therefore, the quantum dot material provided by the invention can rationalize the core-shell structure to be reasonable, so that the energy levels of the quantum dot and the hole transport material are matched, and the fluorescence quantum yield is finally improved.
According to the quantum dot light-emitting diode provided by the invention, the light-emitting layer is made of the quantum dot material, so that the energy levels of the quantum dot and the hole transport material can be matched, and the fluorescence quantum yield is finally improved.
The light-emitting device provided by the invention contains the quantum dot light-emitting diode, so that the obtained light-emitting device has better fluorescence quantum yield.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a flow chart of a preparation process of a quantum dot material provided by an embodiment of the invention;
FIG. 2 is a fluorescence spectrum of a quantum dot material provided in example 1 of the present invention;
FIG. 3 is a fluorescence spectrum of a quantum dot material provided in example 2 of the present invention;
FIG. 4 is a fluorescence spectrum of a quantum dot material provided in example 3 of the present invention;
fig. 5 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
As shown in fig. 1, a first aspect of an embodiment of the present invention provides a method for preparing a quantum dot material, including the following steps:
s01, preparing a precursor solution containing zinc, cadmium and sulfur, and heating to a first reaction temperature in an inert atmosphere to obtain Cd1-xZnxS quantum dot core solution;
s02, in an inert atmosphere, at a second reaction temperature, adding Cd into the solution1-xZnxAdding a first sulfur precursor, a first cadmium precursor and a first zinc precursor into the S quantum dot core solution, carrying out a first shell layer reaction, and adding Cd into the solution1-xZnxSurface growth Cd of S quantum dot core1-yZnyS shell layer to obtain Cd1-xZnxS/Cd1-yZnyS quantum dot solution;
s03, in an inert atmosphere, at a third reaction temperature, carrying out reaction on the Cd1-xZnxS/Cd1-yZnyAdding a second sulfur precursor, a second cadmium precursor and a second zinc precursor into the S quantum dot solution, carrying out shell layer reaction, and adding Cd into the solution1-xZnxS/Cd1-yZnySurface growth Cd of S quantum dot1-zZnzS shell layer, preparing Cd1-xZnxS/Cd1-yZnyS/Cd1-zZnzS quantum dots;
wherein, the value ranges of x, y and z satisfy: x is more than or equal to 0 and less than y and z is less than or equal to 1.
According to the preparation method of the blue quantum dot material, provided by the embodiment of the invention, the shell layers formed by Cd, Zn and S elements are prepared layer by layer, and the core-shell structure quantum dot with continuously gradually changed Cd and Zn is obtained by regulating the addition amount of the cadmium precursor solution and the zinc precursor solution in the preparation process of the shell layers. Cd prepared by the method1-xZnxS/Cd1-yZnyS/Cd1-zZnzIn the S quantum dots, the Zn content is higher and higher from inside to outside. The core-shell quantum dot with the structure has wider forbidden band width of a shell material, effectively confines electrons and holes in a core, and improves the fluorescence quantum yield of the quantum dot; in the shell structure, the energy level is gradually changed along with the increase of the forbidden bandwidth of the materials from inside to outside along with the proportion of zinc, and the final energy level of the quantum dots can be adjusted by simply adjusting the components of the shell, so that the quantum dots are effectively matched and adapted to hole transport materials with different energy levels. In conclusion, the preparation method of the blue quantum dot material provided by the invention can be used for preparing the quantum dot which has high fluorescence quantum yield and reasonable core-shell structure and is matched with the energy level of the hole transport material, thereby promoting the development of the blue quantum dot light-emitting diode device.
Specifically, in step S01, the precursor solution of zinc, cadmium and sulfur refers to a solution containing Cd1-xZnxA zinc source, a cadmium source and a sulfur source required by the S quantum dot.
In some embodiments, the method of configuring a precursor solution comprising zinc, cadmium, sulfur is: under inert atmosphere, putting zinc salt and cadmium salt into a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a precursor solution of zinc and cadmium; adding a sulfur source precursor into the zinc and cadmium precursor solution to prepare the precursor solution containing zinc, cadmium and sulfur; wherein the hydrocarbon is an alkane or alkene. In the method for preparing the precursor solution containing zinc, cadmium and sulfur provided by this embodiment, a mixed solution of zinc salt and cadmium salt is prepared first, that is, a cation precursor solution is prepared first, and after the cations are completely dissolved, a sulfur source precursor solution is added. By the method, the two cations can be uniformly dispersed and in a proper reaction state, and then the cation precursor can uniformly react with the sulfur source precursor after the sulfur source precursor is added.
Wherein, a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature is adopted as a dissolving solvent of the zinc salt and the cadmium salt, wherein the hydrocarbon is alkane or alkene. On one hand, the mixed solvent of fatty acid and alkane or alkene has better solubility to zinc salt and cadmium salt, and on the other hand, the mixed solvent of fatty acid and alkane or alkene, especially the mixed solvent of high boiling point fatty acid and alkane or alkene, can ensure that the reaction is carried out in a stable medium system. In the embodiments of the present invention, the high boiling point alkane or alkene is typically a long chain alkane or a long chain alkene.
Wherein, the zinc salt and the cadmium salt are placed in a mixed solvent of fatty acid and alkane or a mixed solvent of fatty acid and alkene, the boiling point of which is higher than the reaction temperature, and the zinc salt and the cadmium salt can be placed in the mixed solvent together; or preparing a zinc salt solution and a cadmium salt solution by respectively using the mixed solution as a solvent, and mixing the zinc salt solution and the cadmium salt solution to obtain the cadmium-doped zinc oxide material; the mixed solution can also be used as a solvent, a zinc salt (or cadmium salt) solution is prepared first, and then the cadmium salt (or zinc salt) is added.
Wherein, the heating condition with the temperature range of 100-260 ℃ can further promote the dissolution of zinc salt and cadmium salt in the mixed solvent of fatty acid and alkane or alkene, so that the zinc salt and cadmium salt are in a complete dissolution state in a solvent system, and a favorable reaction state is provided for the reaction with a sulfur source precursor.
In some embodiments, the concentration of the zinc and the cadmium in the precursor solution comprising zinc, cadmium and sulfur is 0.02mmol/ml to 0.5 mmol/ml. Because the nucleation process of the quantum dots is a curing and growing process, in the reaction process, if the concentration of reactants such as the sum of the concentrations of zinc and cadmium is too high or too low, the concentration of reaction activated particles is different, uniform nano particles cannot be formed in the curing process, the obtained quantum dots have the phenomenon of nonuniform size or morphology, the phenomenon is reflected in a spectrum, namely the broadening and asymmetry of a fluorescence emission spectrum, and meanwhile, the problems of yield reduction of the quantum dots and the like are often accompanied.
In some embodiments, in the precursor solution comprising zinc, cadmium and sulfur, the ratio of zinc to cadmium in a molar ratio of 0.1: 1-10: 1, wherein the molar ratio of sulfur to cadmium is 1: 1-10: 11 preparing a precursor solution containing zinc, cadmium and sulfur.
In the embodiment of the invention, Cd is obtained by heating to the reaction temperature under the inert atmosphere1-xZnxIn the step of the S quantum dot core solution, the reaction temperature ranges from 270 ℃ to 310 ℃, and the reaction time ranges from 5 minutes to 30 minutes. Under the condition of the temperature, cadmium and zinc are alloyed and reacted, and simultaneously, cadmium and sulfur are reacted to generate Cd1-xZnxAnd S. If the reaction temperature is too low, cadmium-zinc alloying is difficult to realize, so Cd cannot be obtained by reaction1-xZnxAnd S. With the increase of the temperature, the better the crystallinity of the obtained quantum dot is, and the stability is enhanced. However, if the reaction temperature is too high, higher than 310 ℃, the solvent used as the reaction medium is volatilized, which is unfavorable for the reaction.
In a preferred embodiment, precursor solution containing zinc, cadmium and sulfur is prepared and heated to reaction temperature under inert atmosphere to obtain Cd1-xZnxThe step of preparing the S quantum dot core solution comprises the following steps: under inert atmosphere, putting zinc salt and cadmium salt into a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a precursor solution of zinc and cadmium; continuously heating to the reaction temperature, adding a sulfur source precursor into the precursor solution of the zinc and the cadmium, and reacting to prepare the Cd1-xZnxAn S quantum dot core. In the method, after heating and dissolving zinc salt and cadmium salt, further heating to reaction temperature to prepare for synthesis of quantum dots, and after adding a sulfur source precursor, reacting the sulfur source at a proper temperature to generate Cd1-xZnxAn S quantum dot core. If the zinc salt, the cadmium salt and the sulfur source are heated together, the zinc salt, the cadmium salt and the sulfur source also react in the heating process, but because the activity of cadmium is far higher than that of zinc at low temperature, cadmium sulfide is generated at first at low temperature, so that the sulfur can not better react with alloyed zinc and cadmium to generate zinc-cadmium-sulfur alloy quantum dots, and part of finally obtained products are not Cd1-xZnxAnd the S quantum dot core reduces the purity of the product. More preferably, the concentration range of the zinc and cadmium precursor solution is 0.02 mmol/mL-0.5 mmol/mL.
In the step S02, the first sulfur precursor, the first cadmium precursor, and the first zinc precursor are added in an inert atmosphere at the reaction temperature to prepare the first shell layer. And adding a first sulfur precursor, a first cadmium precursor and a first zinc precursor according to the molar weight ratio of the sulfur element, the cadmium element and the zinc element in the prepared first shell in the step of adding the first sulfur precursor, the first cadmium precursor and the first zinc precursor in the inert atmosphere at the first reaction temperature. Preferably, the first sulfur precursor solution, the first cadmium precursor solution and the first zinc precursor solution are added according to the molar weight ratio of the sulfur element, the cadmium element and the zinc element in the prepared first shell.
In some embodiments, the first sulfur precursor is prepared by a method comprising: under inert atmosphere, dissolving sulfur simple substance in at least one of alkane, alkene and phosphonic acid with boiling point higher than the first reaction temperature, mixing, and heating and dissolving at 100-200 ℃ to obtain sulfur precursor solution. In the method, at least one of alkane, alkene and phosphonic acid is used as a solvent, which is beneficial to the dissolution of the sulfur salt, and particularly, a sulfur precursor solution with good dissolution performance can be obtained under the heating condition of 100-200 ℃. In a preferred embodiment, elemental sulfur is dissolved in octadecene and mixed, and the mixture is heated and dissolved at a temperature ranging from 100 ℃ to 200 ℃, so that the sulfur precursor solution has better solubility. In some embodiments, the concentration of the sulfur precursor solution ranges from 0.1mmol/mL to 1 mmol/mL.
In some embodiments, the first cadmium precursor is prepared by: under inert atmosphere, dissolving cadmium salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a cadmium precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkane is beneficial to the dissolution of cadmium salt, and particularly, the cadmium precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the cadmium precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL.
In some embodiments, the first zinc precursor is prepared by: under inert atmosphere, dissolving zinc salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a zinc precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkene is beneficial to the dissolution of zinc salt, and particularly, a zinc precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the zinc precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL.
In and for preparing Cd1-xZnxCarrying out a first shell reaction at the same reaction temperature of S quantum dot core and under an inert atmosphere, and carrying out Cd reaction1-xZnxSurface growth of Cd on S quantum dot core1-yZnyS shell layer to obtain Cd1-xZnxS/Cd1-yZnyAnd (3) S quantum dot solution.
In the step S03, the shell layer reaction is carried out at the same second reaction temperature and inert atmosphere as the preparation of the first shell layer, and the Cd is subjected to1-xZnxS/Cd1-yZnySurface growth Cd of S quantum dot1-zZnzS shell layer, preparing Cd1-xZnxS/Cd1- yZnyS/Cd1-zZnzAnd (4) S quantum dots. Adding a second sulfur precursor, a second cadmium precursor and a second zinc precursor in an inert atmosphere at the second reaction temperature according to the prepared Cd1-zZnzAnd adding a second sulfur precursor, a second cadmium precursor and a second zinc precursor according to the molar weight ratio of the sulfur element, the cadmium element and the zinc element in the shell layer of the S shell layer. Preferably, Cd obtained according to the preparation1-zZnzAnd adding a second sulfur precursor solution, a second cadmium precursor solution and a second zinc precursor solution according to the molar weight ratio of the sulfur element, the cadmium element and the zinc element in the shell layer of the S shell layer.
In some embodiments, in saidBetween the step of performing the first shell reaction and the step of performing the outer shell reaction, that is, between the step S02 and the step S03, the method further includes: at a fourth reaction temperature, preparing the obtained Cd in the previous step1- xZnxS/Cd1-yZnyAdding a third sulfur precursor, a third cadmium precursor and a third zinc precursor into the S quantum dot solution to perform a second shell layer reaction, and reacting the Cd with a second cadmium precursor1-xZnxS/Cd1-yZnyThe S quantum dots are sequentially provided with a second shell layer; sequentially forming shell layers on the second shell layer from inside to outside according to the same method as the second shell layer until reaching an Nth shell layer; and from the Cd1-yZnyAnd in the preparation process from the S shell layer to the N shell layer, the addition amount of the third cadmium precursor is sequentially reduced, and the addition amount of the third zinc precursor is sequentially increased, wherein N is less than or equal to 8. According to the core-shell quantum dot obtained by arranging the multiple layers of continuous gradient transition layers, the forbidden bandwidth of the shell material is wide, electrons and holes are effectively confined in the core, and the fluorescence quantum yield of the interest rate quantum dot is improved.
Wherein, in each shell reaction, the fourth reaction temperature is equal to that of the previous step for preparing Cd1-xZnxS quantum dot core, Cd1- yZnyS shell and Cd1-zZnzThe temperature of the S shell layer is the same. In some embodiments, the fourth reaction temperature ranges from 270 ℃ to 310 ℃ and the reaction time ranges from 5 minutes to 30 minutes in each shell reaction.
In some embodiments, the second sulfur precursor is prepared by: under inert atmosphere, dissolving sulfur simple substance in at least one of alkane, alkene and phosphonic acid with boiling point higher than the reaction temperature, mixing, and heating and dissolving at 100-200 ℃ to obtain sulfur precursor solution. In the method, at least one of alkane, alkene and phosphonic acid is used as a solvent, which is beneficial to the dissolution of the sulfur salt, and particularly, a sulfur precursor solution with good dissolution performance can be obtained under the heating condition of 100-200 ℃. In a preferred embodiment, elemental sulfur is dissolved in octadecene and mixed, and the mixture is heated and dissolved at a temperature ranging from 100 ℃ to 200 ℃, so that the sulfur precursor solution has better solubility. In some embodiments, the concentration of the sulfur precursor solution ranges from 0.1mmol/mL to 1 mmol/mL.
In some embodiments, the second cadmium precursor is prepared by: under inert atmosphere, dissolving cadmium salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a cadmium precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkane is beneficial to the dissolution of cadmium salt, and particularly, the cadmium precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the cadmium precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL.
In some embodiments, the second zinc precursor is prepared by: under inert atmosphere, dissolving zinc salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a zinc precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkene is beneficial to the dissolution of zinc salt, and particularly, a zinc precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the zinc precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL.
In some embodiments, the third sulfur precursor is prepared by: under inert atmosphere, dissolving sulfur simple substance in at least one of alkane, alkene and phosphonic acid with boiling point higher than the reaction temperature, mixing, and heating and dissolving at 100-200 ℃ to obtain sulfur precursor solution. In the method, at least one of alkane, alkene and phosphonic acid is used as a solvent, which is beneficial to the dissolution of the sulfur salt, and particularly, a sulfur precursor solution with good dissolution performance can be obtained under the heating condition of 100-200 ℃. In a preferred embodiment, elemental sulfur is dissolved in octadecene and mixed, and the mixture is heated and dissolved at a temperature ranging from 100 ℃ to 200 ℃, so that the sulfur precursor solution has better solubility. In some embodiments, the concentration of the third sulfur precursor solution ranges from 0.1mmol/mL to 1 mmol/mL.
In some embodiments, the third cadmium precursor is prepared by: under inert atmosphere, dissolving cadmium salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a cadmium precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkane is beneficial to the dissolution of cadmium salt, and particularly, the cadmium precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the third cadmium precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL.
In some embodiments, the third zinc precursor is prepared by: under inert atmosphere, dissolving zinc salt in a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a zinc precursor solution, wherein the hydrocarbon is alkane or alkene. In the method, the mixed solvent of fatty acid and alkane or the mixed solvent of fatty acid and alkene is beneficial to the dissolution of zinc salt, and particularly, a zinc precursor solution with good dissolution performance can be obtained under the heating condition of 100-260 ℃. In some embodiments, the concentration of the third zinc precursor solution ranges from 0.1mmol/mL to 0.5 mmol/mL. Further, after the reaction is finished, the method also comprises the steps of precipitating, centrifugally separating and drying the product, and finally the target quantum dot is obtained. In some embodiments, after the reaction is complete, an excess of polar reagent is added to the solution, and the precipitate is collected after centrifugation; dissolving the precipitate in a non-polar solvent, adding a polar solvent for precipitation, repeating the steps for multiple times, and collecting the quantum dots. Wherein the non-polar solvent is selected from but not limited to chloroform, chlorobenzene, benzene, toluene, acetonitrile, n-hexane, n-octane, cyclohexane; the polar solvent is selected from but not limited to methanol, ethanol, acetone.
It should be noted that in the preparation method of the quantum dot material according to the embodiment of the present invention, the inert atmosphere refers to a gas environment including a nitrogen atmosphere and a helium atmosphere, but is not limited thereto. The alkane or alkene used to dissolve the sulfur source, cadmium salt, zinc salt may be selected from dodecane, tetradecane, octadecane, tetracosane, octadecene, liquid paraffin; the phosphonic acid used to dissolve the sulfur source may be selected from diphenylphosphine, tributylphosphine, trioctylphosphine, hexylphosphonic acid; the fatty acid used for dissolving zinc salt and cadmium salt can be oleic acid, octadecyl acid and tetradecanoic acid. The cadmium salt or source is selected from, but not limited to, CdO, Cd (Ac)2、CdSt2、CdCl2(ii) a The zinc salt or source is selected from, but not limited to, ZnO, Zn (Ac)2、ZnSt2、ZnCl2。
In a second aspect, embodiments of the present invention provide quantum dot materials comprising Cd1-xZnxS quantum dot core of Cd1-xZnxCd formed on surface of S quantum dot core1-yZnyS shell layer, and Cd1-yZnyCd formed on surface of S shell1-zZnzAnd (2) an S shell layer, wherein the value ranges of x, y and z meet the following requirements: x is more than or equal to 0<y<z≤1。
The quantum dot material provided by the embodiment of the invention has higher and higher Zn content from inside to outside. The core-shell quantum dot with the structure has wider forbidden band width of a shell material, effectively confines electrons and holes in a core, and improves the fluorescence quantum yield of the quantum dot; in the shell structure, the energy level is gradually changed along with the increase of the forbidden bandwidth of the materials from inside to outside along with the proportion of zinc, and the final energy level of the quantum dots can be adjusted by simply adjusting the components of the shell, so that the quantum dots are effectively matched and adapted to hole transport materials with different energy levels. Therefore, the quantum dot material provided by the invention can rationalize the core-shell structure to be reasonable, so that the energy levels of the quantum dot and the hole transport material are matched, and the fluorescence quantum yield is finally improved.
In some embodiments, the Cd is1-yZnyS shell layer and the Cd1-zZnzAnd N-1 intermediate shell layers are further included between the S shell layers, and in the quantum dot material, the cadmium content is sequentially reduced and the zinc content is sequentially increased from outside to outside through the intermediate shell layers, wherein N is a positive integer less than or equal to 8.
In some embodiments, the quantum dot material is a blue quantum dot material.
As shown in fig. 2, a third aspect of the embodiments of the present invention provides a quantum dot light emitting diode, including an anode and a cathode that are oppositely disposed, and a quantum dot light emitting layer disposed between the anode and the cathode, where a material of the quantum dot light emitting layer includes the quantum dot material described above, or a material of the quantum dot light emitting layer includes the quantum dot material prepared by the method described above.
According to the quantum dot light-emitting diode provided by the embodiment of the invention, as the light-emitting layer is made of the quantum dot material, the energy levels of the quantum dot and the hole transport material can be matched, and the fluorescence quantum yield is finally improved.
Specifically, the quantum dot light emitting diode according to the embodiment of the present invention has a positive structure and an inversion structure.
In one embodiment, a positive structure quantum dot light emitting diode includes an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, and the anode is disposed on a substrate. Furthermore, an electron functional layer such as an electron injection layer, an electron transport layer, a hole blocking layer and the like can be arranged between the cathode and the electron transport layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of the positive-type structure device, the quantum dot light emitting diode includes a substrate, an anode disposed on a surface of the substrate, the hole injection layer disposed on a surface of the anode, a hole transport layer disposed on a surface of the hole injection layer, a quantum dot light emitting layer disposed on a surface of the hole transport layer, an electron transport layer disposed on a surface of the quantum dot light emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, an inverted structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, and the cathode disposed on a substrate. Furthermore, an electron functional layer such as an electron injection layer, an electron transport layer, a hole blocking layer and the like can be arranged between the cathode and the electron transport layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of the device with the inverted structure, the quantum dot light emitting diode includes a substrate, a cathode disposed on a surface of the substrate, an electron transport layer disposed on a surface of the cathode, a quantum dot light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the quantum dot light emitting layer, an electron injection layer disposed on a surface of the hole transport layer, and an anode disposed on a surface of the electron injection layer.
A fourth aspect of the embodiments of the present invention provides a light emitting device, including a quantum dot light emitting diode, where the quantum dot light emitting diode is the above-mentioned quantum dot light emitting diode.
The light-emitting device provided by the embodiment of the invention contains the quantum dot light-emitting diode, so that the obtained light-emitting device has better fluorescence quantum yield.
The following description will be given with reference to specific examples.
Example 1
A quantum dot material is prepared by the following steps:
(1) preparing a sulfur precursor solution: 0.064g of sulfur and 10ml of octadecene were put in a three-necked flask, stirred at a temperature of 25 ℃, evacuated, and then supplemented with nitrogen gas, and the process was repeated three times. Heating to 120 ℃, and stirring until the sulfur simple substance is completely dissolved to obtain a sulfur precursor solution with the concentration of 0.2 mmol/ml.
(2) Preparing a precursor of cadmium: under the protection of nitrogen, 0.128g of cadmium oxide, 1ml of oleic acid and 9ml of octadecene are mixed and stirred to be uniformly mixed; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.1 mmol/ml.
(3) Preparation of a zinc precursor: under the protection of nitrogen, 0.081g of zinc oxide, 1ml of oleic acid and 4ml of octadecene are mixed and stirred to be uniformly mixed; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.2 mmol/ml.
(4) 0.102g of CdO, 0.098g of ZnO, 2ml of OA, and 18ml of ODE were placed in a three-necked flask, and a mixed solution was prepared by stirring at 25 ℃ and then evacuated, followed by supplying nitrogen gas and repeating three times. Heating to raise the temperature to 200 ℃ of the mixed solution, and stirring until the CdO and the ZnO are completely dissolved; heating to 270 ℃, injecting 5ml of sulfur precursor solution in the step (1) into the solution in the step (4), and reacting for 20 minutes to obtain Cd0.8Zn0.2S quantum dot core solution; to Cd0.8Zn0.2Adding cadmium, zinc and sulfur precursors in the steps (1), (2) and (3) into the S quantum dot core solution, wherein the molar ratio of the cadmium, the zinc and the sulfur precursors is 0.5: 0.5: 1, slowly injecting sulfur in the solution to obtain Cd, wherein the sulfur is 0.5mmol0.8Zn0.2S/Cd0.5Zn0.5S, preparing a core-shell quantum dot solution; to Cd0.8Zn0.2S/Cd0.5Zn0.5And (3) adding cadmium, zinc and sulfur precursors in the step (1), the step (2) and the step (3) into the S core-shell quantum dot solution, wherein the molar ratio is 0.2: 0.8: 1, slowly injecting sulfur in the solution to obtain Cd, wherein the sulfur is 0.5mmol0.8Zn0.2S/Cd0.5Zn0.5S/Cd0.2Zn0.8And (3) S core-shell quantum dot solution. After cooling, adding excessive polar solvent methanol into the solution, and pouring out the supernatant after centrifugation; dissolving the precipitate in nonpolar solvent n-hexane, adding excessive methanol, and centrifuging to precipitate; repeating the steps for three times, and finally dissolving the quantum dots in a non-polar solvent.
Example 1 Quantum dot Material and Cd0.8Zn0.2The fluorescence spectrum of the S quantum dot core is shown in FIG. 3, which is seen from FIG. 3, and Cd0.8Zn0.2Comparing S quantum dot core, embodiment 1 of the invention is Cd0.8Zn0.2S quantum dot core cladding Cd0.5Zn0.5S/Cd0.2Zn0.8After the S shell layer is formed, the fluorescence Quantum Yield (QY) of the quantum dots is improved from 30% to 92%; the fluorescence peak position was red-shifted by 3nm, and the half-peak width was broadened by 3 nm.
Example 2
A quantum dot material is prepared by the following steps:
(1) preparing a sulfur precursor solution: 0.064g of sulfur and 10ml of TOP were placed in a three-necked flask, stirred at a temperature of 25 ℃ and evacuated, then nitrogen gas was added, and the process was repeated three times. Heating to 120 ℃, and stirring until the sulfur simple substance is completely dissolved to obtain a sulfur precursor solution with the concentration of 0.2 mmol/ml.
(2) Preparing a precursor of cadmium: under the protection of nitrogen, 0.128g of cadmium oxide, 1ml of oleic acid and 9ml of octadecene are mixed and stirred to be uniformly mixed; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.1 mmol/ml.
(3) Preparation of a zinc precursor: under the protection of nitrogen, 0.081g of zinc oxide, 1ml of oleic acid and 4ml of octadecene are mixed and stirred to be uniformly mixed; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.2 mmol/ml.
(4) 0.102g of CdO, 0.098g of ZnO, 2ml of OA, and 18ml of ODE were placed in a three-necked flask, stirred at 25 ℃ and then evacuated and then charged with nitrogen gas, and the process was repeated three times. Heating to raise the temperature to 200 ℃ of the mixed solution, and stirring until the CdO and the ZnO are completely dissolved; heating to 270 ℃, injecting 5ml of sulfur precursor solution in the step (1) into the solution in the step (4), and reacting for 20 minutes to obtain Cd0.8Zn0.2S quantum dot core solution; to Cd0.8Zn0.2Adding cadmium, zinc and sulfur precursors in the steps (1), (2) and (3) into the S quantum dot core solution, wherein the molar ratio of the cadmium, the zinc and the sulfur precursors is 0.4: 0.6: 1, slowly injecting sulfur in the solution to obtain Cd, wherein the sulfur is 0.5mmol0.8Zn0.2S/Cd0.4Zn0.6S, preparing a core-shell quantum dot solution; to Cd0.8Zn0.2S/Cd0.4Zn0.6Adding zinc and sulfur precursors in 2 and 3 into the S core-shell quantum dot solution, and mixing the two materials according to a molar ratio of 1: 1, slowly injecting sulfur in the solution to obtain Cd, wherein the sulfur is 0.5mmol0.8Zn0.2S/Cd0.4Zn0.6S/ZnS core-shell quantum dot solution. After cooling, adding excessive polar solvent methanol into the solution, and pouring out the supernatant after centrifugation; dissolving the precipitate in nonpolar solvent n-hexane, adding excessive methanol, and centrifuging to precipitate; repeating the steps for three times, and finally dissolving the quantum dots in a non-polar solvent.
Example 2 Quantum dot Material and Cd0.8Zn0.2The fluorescence spectrum of the S quantum dot core is shown in FIG. 4, which is shown in FIG. 4, and is related to Cd0.8Zn0.2Comparing S quantum dot core, embodiment 1 of the invention is Cd0.8Zn0.2S quantum dot core cladding Cd0.4Zn0.6After an S/ZnS shell layer is adopted, the fluorescence Quantum Yield (QY) of the quantum dots is improved from 30% to 95%; the fluorescence peak position is red-shifted by 2nm, and the half-peak width is widened by 2 nm.
Example 3
A quantum dot material is prepared by the following steps:
(1) preparing a sulfur precursor solution: 0.064g of sulfur and 10ml of octadecene were put in a three-necked flask, stirred at a temperature of 25 ℃, then evacuated and supplemented with nitrogen gas, and the process was repeated three times. Heating to 120 ℃, and stirring until the sulfur simple substance is completely dissolved to obtain a sulfur precursor solution with the concentration of 0.2 mmol/ml.
(2) The preparation of the precursor of cadmium is as follows: under the protection of nitrogen, 0.128g of cadmium oxide, 1ml of oleic acid and 9ml of octadecene are mixed and stirred to be uniformly mixed; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.1 mmol/ml.
(3) The zinc precursor was prepared as follows: under the protection of nitrogen, 0.183g of zinc acetate, 1ml of oleic acid and 4ml of octadecene are mixed and stirred uniformly; heating and stirring at 240 ℃ to dissolve, and obtaining a precursor solution of cadmium with the concentration of 0.2 mmol/ml.
(4) 0.128g of CdO, 0.183g of zinc acetate, 2ml of OA and 18ml of ODE were placed in a three-necked flask, stirred at 25 ℃ and then evacuated and supplemented with nitrogen, and the process was repeated three times. Heating to raise the temperature to 200 ℃ of the mixed solution, and stirring until the CdO and the ZnO are completely dissolved; heating to 270 ℃, injecting 5ml of the sulfur precursor solution in the step (1) into the solution in the step (4), and reacting for 20 minutes to obtain a CdS quantum dot core solution; adding cadmium, zinc and sulfur precursors in the steps (1), (2) and (3) into the CdS quantum dot core solution, wherein the molar ratio of the cadmium precursors to the zinc precursors to the sulfur precursors is 0.5: 0.5: 1, slowly injecting sulfur in the solution to 0.5mmol to obtain CdS/Cd0.5Zn0.5S, preparing a core-shell quantum dot solution; to CdS/Cd0.5Zn0.5S core-shell quantumAdding cadmium, zinc and sulfur precursors in the step (1), the step (2) and the step (3) into the solution, and mixing the cadmium, the zinc and the sulfur precursors according to a molar ratio of 0.2: 0.8: 1, slowly injecting sulfur in the solution to 0.5mmol to obtain CdS/Cd0.5Zn0.5S/Cd0.2Zn0.8And (3) S core-shell quantum dot solution. After cooling, adding excessive polar solvent methanol into the solution, and pouring out the supernatant after centrifugation; dissolving the precipitate in nonpolar solvent n-hexane, adding excessive methanol, and centrifuging to precipitate; repeating the steps for three times, and finally dissolving the quantum dots in a non-polar solvent.
The fluorescence spectrum of the quantum dot material and the CdS quantum dot core provided in embodiment 3 is shown in FIG. 5, and as can be seen from FIG. 5, compared with the CdS quantum dot core, in embodiment 1 of the present invention, Cd is coated on the CdS quantum dot core0.5Zn0.5S/Cd0.2Zn0.8After the S shell layer, the fluorescence Quantum Yield (QY) of the quantum dots is improved from 7% to 94%, the fluorescence peak position is red-shifted by 32nm, and the half-peak width is shrunk by 4 nm.
In the above examples of the present invention, the fluorescence Quantum Yield (QY) was obtained by integrating the fluorescence intensity of the quantum dot solution and comparing it with the known standard fluorescence quantum yield (coumarin 540, fluorescence quantum yield 78% in ethanol solution; rhodamine 590, fluorescence quantum yield 95% in ethanol solution). Transmission Electron Microscopy (TEM) JEM-2010, with an acceleration voltage of 200 kV.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (14)
1. The preparation method of the quantum dot material is characterized by comprising the following steps of:
preparing a precursor solution containing zinc, cadmium and sulfur, and heating the precursor solution to a first reaction temperature in an inert atmosphere to obtain Cd1-xZnxS quantum dot core solution;
under inert atmosphere at a second reaction temperature, under the action of the carrier gas, and in the presence of the Cd1-xZnxAdding a first sulfur precursor and a first sulfur precursor into the S quantum dot core solutionCadmium precursor and first zinc precursor are subjected to first shell reaction, and Cd is obtained1-xZnxSurface growth Cd of S quantum dot core1-yZnyS shell layer to obtain Cd1-xZnxS/Cd1-yZnyS quantum dot solution;
under inert atmosphere at a third reaction temperature in the presence of Cd1-xZnxS/Cd1-yZnyAdding a second sulfur precursor, a second cadmium precursor and a second zinc precursor into the S quantum dot solution, and carrying out shell layer reaction on the S quantum dot solution, wherein Cd is1-xZnxS/Cd1-yZnySurface growth Cd of S quantum dot1-zZnzS shell layer, preparing Cd1-xZnxS/Cd1-yZnyS/Cd1-zZnzS quantum dots;
wherein, the value ranges of x, y and z satisfy: x is more than or equal to 0 and less than y and z is less than or equal to 1.
2. The method of preparing a quantum dot material according to claim 1, wherein between the step of performing the first shell reaction and the step of performing the outer shell reaction, further comprising:
at a fourth reaction temperature, preparing the obtained Cd in the previous step1-xZnxS/Cd1-yZnyAdding a third sulfur precursor, a third cadmium precursor and a third zinc precursor into the S quantum dot solution to perform a second shell layer reaction, and reacting the Cd with a second cadmium precursor1-xZnxS/Cd1-yZnyThe S quantum dots are sequentially provided with a second shell layer; sequentially forming shell layers on the second shell layer from inside to outside according to the same method as the second shell layer until reaching an Nth shell layer; and from the Cd1-yZnyAnd in the preparation process from the S shell layer to the N shell layer, the addition amount of the third cadmium precursor is sequentially reduced, and the addition amount of the third zinc precursor is sequentially increased, wherein N is less than or equal to 8.
3. The method of claim 1 or 2, wherein the first reaction temperature, the second reaction temperature, and the third reaction temperature range from 270 ℃ to 310 ℃ and the reaction time is from 5 minutes to 30 minutes.
4. The method of claim 2, wherein the fourth reaction temperature is 270 ℃ to 310 ℃ and the reaction time is 5 minutes to 30 minutes.
5. The method for preparing a quantum dot material according to claim 1, wherein the method for preparing the precursor solution comprising zinc, cadmium and sulfur comprises the following steps: under inert atmosphere, putting zinc salt and cadmium salt into a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a precursor solution containing zinc and cadmium; adding a sulfur source precursor into the zinc and cadmium precursor solution to prepare the precursor solution containing zinc, cadmium and sulfur; wherein the hydrocarbon is an alkane or alkene.
6. The method for preparing the quantum dot material of claim 5, wherein a precursor solution comprising zinc, cadmium and sulfur is prepared, and the precursor solution is heated to a reaction temperature under an inert atmosphere to obtain Cd1-xZnxThe step of preparing the S quantum dot core solution comprises the following steps:
under inert atmosphere, putting zinc salt and cadmium salt into a mixed solvent of fatty acid and hydrocarbon with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a precursor solution of zinc and cadmium; continuously heating to the reaction temperature, adding a sulfur source precursor into the precursor solution of the zinc and the cadmium, and reacting to prepare the Cd1-xZnxAn S quantum dot core.
7. The method of claim 5 or 6, wherein the concentration of the zinc and cadmium precursor solution is in the range of 0.02mmol/mL to 0.5 mmol/mL.
8. The method of preparing a quantum dot material according to claim 2,
the preparation methods of the first sulfur precursor, the second sulfur precursor and the third sulfur precursor respectively comprise the following steps: under inert atmosphere, dissolving sulfur simple substance in at least one of alkane, alkene and phosphonic acid with boiling point higher than the reaction temperature, mixing, and heating and dissolving at 100-200 ℃ to obtain sulfur precursor solution; and/or
The preparation methods of the first cadmium precursor, the second cadmium precursor and the third cadmium precursor respectively comprise the following steps: under inert atmosphere, dissolving cadmium salt in a mixed solvent of fatty acid and alkane or alkene with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a cadmium precursor solution; and/or
The preparation methods of the first zinc precursor, the second zinc precursor and the third zinc precursor respectively comprise the following steps: under inert atmosphere, dissolving zinc salt in a mixed solvent of fatty acid and alkane or alkene with the boiling point higher than the reaction temperature, and heating and dissolving at the temperature of 100-260 ℃ to obtain a zinc precursor solution.
9. The method for preparing a quantum dot material according to claim 8, wherein the concentration ranges of the first sulfur precursor solution, the second cadmium precursor and the third cadmium precursor are 0.1mmol/mL to 1mmol/mL, respectively; and/or
The concentration ranges of the first cadmium precursor solution, the second cadmium precursor and the third cadmium precursor are respectively 0.1 mmol/mL-0.5 mmol/mL; and/or
The concentration ranges of the first zinc precursor solution, the second zinc precursor and the third zinc precursor are 0.1 mmol/mL-0.5 mmol/mL.
10. A quantum dot material, comprising Cd1-xZnxS quantum dot core of Cd1- xZnxS quantum dot nuclear tableSurface formed Cd1-yZnyS shell layer, and Cd1-yZnyCd formed on surface of S shell1-zZnzAnd (2) an S shell layer, wherein the value ranges of x, y and z meet the following requirements: x is more than or equal to 0<y<z≤1。
11. The quantum dot material of claim 10, wherein the Cd is in the form of Cd1-yZnyS shell layer and the Cd1- zZnzAnd N-1 intermediate shell layers are further included between the S shell layers, and in the quantum dot material, the cadmium content is sequentially reduced and the zinc content is sequentially increased from outside to outside through the intermediate shell layers, wherein N is a positive integer less than or equal to 8.
12. The quantum dot material of claim 10 or 11, wherein the quantum dot material is a blue quantum dot material.
13. A quantum dot light emitting diode comprising an anode and a cathode disposed opposite to each other, and a quantum dot light emitting layer disposed between the anode and the cathode, wherein a material of the quantum dot light emitting layer comprises the quantum dot material according to any one of claims 10 to 12, or a material of the quantum dot light emitting layer comprises the quantum dot material prepared by the method according to any one of claims 1 to 9.
14. A light emitting device comprising a quantum dot light emitting diode, wherein the quantum dot light emitting diode is the quantum dot light emitting diode of claim 13.
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