CN112980428A - Core-shell structure quantum dot, and preparation method and application thereof - Google Patents
Core-shell structure quantum dot, and preparation method and application thereof Download PDFInfo
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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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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The application discloses a quantum dot with a core-shell structure, and a preparation method and application thereof. The quantum dots with the core-shell structure comprise first core-shell quantum dots, wherein the first core-shell quantum dots comprise quantum dot cores and at least two inner shell layers coated outside the quantum dot cores, and the forbidden bandwidth of each layer of material of the first core-shell quantum dots is sequentially increased from inside to outside along the radial direction; and the first shell layer is directly coated outside the first core-shell quantum dots, and the forbidden bandwidth of the material of the first shell layer is smaller than that of the material of the outermost layer of the first core-shell quantum dots. The forbidden bandwidth of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction, namely the forbidden bandwidth of the shell material is larger than that of the core material, electrons and holes are confined in the core, and the shell material physically separates the optically active center core from the surrounding medium, so that the water resistance and oxygen stability of the quantum dot can be improved; in addition, a first shell layer with a small forbidden band width is grown outside the first core-shell quantum dot, so that photobleaching can be effectively resisted, and the quantum efficiency is improved.
Description
Technical Field
The application relates to the technical field of quantum dot materials, in particular to a core-shell structure quantum dot, and a preparation method and application thereof.
Background
The quantum dots are also called semiconductor nanocrystals, have the advantages of adjustable light-emitting wavelength, high light-emitting efficiency, good stability and the like, and are widely applied to the fields of display, illumination, biology, solar cells and the like. In recent years, research on II-VI group quantum dot materials such as CdSe and CdS has been greatly advanced, and the efficiency, half-peak width, stability and other properties of the quantum dot materials are greatly improved, so that the quantum dot materials can be applied to the fields of display, biology and the like. However, since Cd is a toxic heavy metal, the european union has made strict regulations on the cadmium content in the goods entering its market, so that the wide application of the cadmium-containing quantum dots is limited, and the research on the environment-friendly cadmium-free quantum dots has never been abandoned. How to improve the performance of the cadmium-free quantum dots is always a research focus and a difficulty in the field.
At present, in cadmium-free quantum dots, III-V group InP-based quantum dots become a research hotspot and are expected to replace Cd-containing quantum dots. However, the InP-based quantum dots have problems such as low fluorescence quantum yield, large emission half-value width (i.e., low color purity), and poor light, heat, and water stability.
Disclosure of Invention
An object of the present application is to provide a core-shell structure quantum dot with good stability, a preparation method thereof, and an application thereof.
In order to achieve the above object, the present application provides a core-shell structure quantum dot, including:
the first core-shell quantum dot comprises a quantum dot core and at least two inner shell layers coated outside the quantum dot core, and the forbidden bandwidth of each layer of material of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction; and
and the first outer shell layer is directly coated outside the first core-shell quantum dot, and the forbidden bandwidth of the first outer shell layer material is smaller than that of the inner shell layer material on the outermost layer of the first core-shell quantum dot.
Furthermore, the core-shell structure quantum dot also comprises a second outer shell layer directly coated outside the first outer shell layer, and the forbidden bandwidth of the material of the second outer shell layer is larger than that of the material of the first outer shell layer.
Furthermore, the quantum dots with the core-shell structure are cadmium-free quantum dots, the quantum dot core is selected from one of III-V family quantum dots or II-III-V family alloy quantum dots, and the material of each inner shell layer is selected from one of II-VI family semiconductor materials.
Further, the first core-shell quantum dot is InZnP/ZnSe/ZnS or InP/ZnSe/ZnS in structure, and the first shell layer is made of ZnSe.
Further, the core-shell structure quantum dot further comprises a second outer shell layer directly coated outside the first outer shell layer, and the second outer shell layer is made of ZnS.
Preferably, the quantum dot core has elemental sulfur.
According to another aspect of the present application, there is also provided a method for preparing a quantum dot with a core-shell structure, including the following steps:
s1, synthesizing a quantum dot core, and coating at least two inner shell layers outside the quantum dot core to obtain a first core-shell quantum dot, wherein the forbidden bandwidth of each layer of material of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction;
and S2, coating a first outer shell layer outside the first core-shell quantum dot to obtain a second core-shell quantum dot, wherein the forbidden bandwidth of the first outer shell layer material is less than that of the inner shell layer material on the outermost layer of the first core-shell quantum dot.
Preferably, after the step S2, the method further includes: step S3, a second shell layer is coated outside the second core-shell quantum dot, and a forbidden bandwidth of the second shell layer material is greater than a forbidden bandwidth of the outermost layer material of the second core-shell quantum dot.
Further, the step S1 includes the following steps:
s11, synthesizing III-V family quantum dot nucleus or II-III-V family alloy quantum dot nucleus in the solution;
s12, adding a first anion precursor and a first cation precursor to the solution containing the quantum dot core, and coating a first layer of the inner shell layer outside the quantum dot core after reaction;
s13, adding a second anion precursor and a second cation precursor into the solution after the reaction of the step S12, and coating a second inner shell layer on the first inner shell layer after the reaction; alternatively, adding a second anion precursor to the solution after the reaction of the step S12, the second anion precursor reacting with the first cation precursor unreacted in the step S12, thereby coating a second layer of the inner shell layer on the first layer of the inner shell layer;
in the step S2, the first core-shell quantum dot, the third cation precursor, and the third anion precursor are mixed and reacted to obtain a product system containing the second core-shell quantum dot;
in the step S3, the second core-shell quantum dot, the fourth cation precursor, and the fourth anion precursor are mixed and reacted to obtain a product system containing the core-shell quantum dot.
Further, in the step S11, after the group iii-v quantum dot core or the group ii-iii-v cadmium-free alloy quantum dot core is synthesized, a sulfur source is added to react for a period of time to obtain the quantum dot core with sulfur element on the surface, preferably, the sulfur source is selected from one or more of S-ODE, S-TBP, and S-TOP.
Further, the ratio of the amount of sulfur element in the sulfur source to the amount of indium element in the indium precursor is (1:3) to (1: 30).
Further, the first cation precursor, the second cation precursor, the third cation precursor, and the fourth cation precursor are zinc precursors, and the first anion precursor, the second anion precursor, the third anion precursor, and the fourth anion precursor are respectively selected from selenium precursors or sulfur precursors.
According to another aspect of the present application, there is also provided a quantum dot composition, including the core-shell structure quantum dot described above, or the core-shell structure quantum dot prepared by the method described above.
According to another aspect of the present application, there is also provided a quantum dot device, including the core-shell structure quantum dot described above, or the core-shell structure quantum dot prepared by the method described above.
Compared with the prior art, the beneficial effect of this application lies in: the forbidden band width of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction, namely the forbidden band width of the shell material is larger than that of the core material, electrons and holes are confined in the core, and the shell material physically separates the optically active center core from the surrounding medium, so that the water resistance and oxygen stability of the quantum dot can be improved; in addition, a first shell layer with a small forbidden band width is grown outside the first core-shell quantum dot, so that photobleaching can be effectively resisted, and the light stability of the quantum dot is improved. The quantum dot with the core-shell structure has the advantages of good stability and high quantum efficiency, and particularly under the condition of high-temperature illumination, the stability is good and the color is small.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a core-shell structured quantum dot;
FIG. 2 is a schematic diagram of another embodiment of a core-shell structured quantum dot;
in the figure: 100. a first core-shell quantum dot; 101. a quantum dot core; 102a/102b, an inner shell layer; 200. a first shell layer; 300. a second outer shell layer.
Detailed Description
The present application is further described below with reference to specific embodiments, and it should be noted that, on the premise of no conflict, any combination between the embodiments or technical features described below may form a new embodiment.
In the description of the present application, it should be noted that, for the terms of orientation, such as "central", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., it indicates that the orientation and positional relationship are based on those shown in the drawings, and is only for the convenience of describing the present application and simplifying the description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and should not be construed as limiting the specific scope of protection of the present application.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
The terms "comprises," "comprising," and "having," and any variations thereof, in the description and claims of this application, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that, when an element such as a layer is referred to as being "coated" on "another element, it can be directly coated on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
As shown in fig. 1 and 2, the present application provides a core-shell quantum dot, including a first core-shell quantum dot 100 and a first outer shell layer 200 directly covering the first core-shell quantum dot 100, where the first core-shell quantum dot 100 includes a quantum dot core 101 and at least two inner shell layers 102 covering the quantum dot core 101, the forbidden bandwidth of each layer of material of the first core-shell quantum dot 100 is sequentially increased from inside to outside along the radial direction, and the forbidden bandwidth of the material of the first outer shell layer 200 is smaller than the forbidden bandwidth of the outermost layer of material of the first core-shell quantum dot 100.
It should be noted that the materials of the layers of the first core-shell quantum dot 100 are understood to include a core and a shell.
In the application, the forbidden bandwidth of the first core-shell quantum dot 100 is sequentially increased from inside to outside along the radial direction, that is, for the first core-shell quantum dot 100, the forbidden bandwidth of the shell material is greater than that of the core material, electrons and holes are confined in the core, and the shell material physically separates the optically active center core from the surrounding medium, so that the water resistance and oxygen stability of the quantum dot can be improved. Aiming at the defect of poor stability of the cadmium-free quantum dot, the first core-shell quantum dot 100 with good stability can be obtained by coating a shell material with a large forbidden band width outside the quantum dot core 101.
In addition, the inventors creatively clad the first shell layer 200 with a smaller forbidden band width than the outermost layer of the first core-shell quantum dot 100 on the first core-shell quantum dot 100, and clad the shell material with a narrow forbidden band width on the material with a larger forbidden band width, so that photobleaching can be effectively resisted, and quantum efficiency can be improved.
The quantum dot with the core-shell structure has the advantages of good stability and high quantum efficiency, and particularly under the condition of high-temperature illumination, the stability is good and the color is small.
In some embodiments, the first housing layer 200 is not covered by other housing layers, as shown in FIG. 1.
In other embodiments, the core-shell quantum dot further includes a second shell layer 300 directly coated on the first shell layer 200, as shown in fig. 2, and the material of the second shell layer 300 has a forbidden band width greater than that of the first shell layer 200. The shell material with a large forbidden band width is directly coated outside the first shell layer 200, which is beneficial to further improving the stability of the core-shell structure quantum dot.
It can be understood that a shell material with a large forbidden band width (relative to the material of the second outer shell layer 300) can be grown outside the second outer shell layer 300 to improve the stability of the core-shell structure quantum dot; shell materials with small forbidden band widths (relative to the materials of the second outer shell layer 300) can also be grown continuously so as to improve the photobleaching resistance of the core-shell structure quantum dots and improve the quantum efficiency and the stability under high-temperature illumination; of course, the second outer shell layer 300 may be coated with no other shell layer.
In some embodiments, the core-shell structure quantum dots are cadmium-free quantum dots, i.e., the quantum dots do not contain cadmium in both the core material and the shell material. The quantum dot with the core-shell structure is particularly suitable for solving the problems of poor stability and low quantum efficiency of the cadmium-free quantum dot.
Further, the quantum dot core 101 is selected from one of group III-V quantum dots or group II-III-V alloy quantum dots, and the material of each inner shell layer 102 is selected from one of group II-VI semiconductor materials. As will be appreciated by those skilled in the art: the III-V group quantum dots refer to quantum dots comprising IIIA group elements and VA group elements; the II-III-V group alloy quantum dots are quantum dots comprising IIB group elements, IIIA group elements and VA group elements; group ii-vi semiconductor materials refer to semiconductor materials that include group iib elements as well as group via elements. In addition, when the core-shell structure quantum dot is a cadmium-free quantum dot, the quantum dot core 101 and each inner shell layer 102 do not contain a group iib cadmium element.
In some embodiments, the first core-shell quantum dot 100 includes two inner shell layers 102a, 102b, the structure of the first core-shell quantum dot 100 may be InZnP/ZnSe/ZnS or InP/ZnSe/ZnS, and the material of the first outer shell layer 200 is ZnSe. Optionally, the first shell layer 200 is directly covered with a second shell layer, and the material of the second shell layer is ZnS.
Further, the surface of the quantum dot core 101 is treated by a sulfur source, so that the surface of the quantum dot core or the inside of the quantum dot core has sulfur, or both the surface of the quantum dot core and the inside of the quantum dot core have sulfur. The inventor finds that after the quantum dot core 101 is treated by the sulfur source, the inner shell layer 102 is coated, which is beneficial to obtaining the first core-shell quantum dot 100 with narrow half-peak width and high quantum efficiency.
The application also provides a preparation method of the core-shell structure quantum dot, which comprises the following steps:
s1, synthesizing a quantum dot core 101, and coating at least two inner shell layers 102 outside the quantum dot core 101 to obtain a first core-shell quantum dot 100, wherein the forbidden bandwidth of each layer of material of the first core-shell quantum dot 100 is sequentially increased from inside to outside along the radial direction;
s2, wrapping the first shell layer 200 outside the first core-shell quantum dot 100 to obtain a second core-shell quantum dot, wherein the forbidden bandwidth of the material of the first shell layer 200 is smaller than that of the outermost layer of the first core-shell quantum dot 100.
In some embodiments, after step S2, step S3 is further included, the second shell layer 300 is wrapped outside the second core-shell quantum dot, and the energy gap of the material of the second shell layer 300 is greater than that of the material of the outermost layer of the second core-shell quantum dot.
In some embodiments, step S1 includes the steps of:
s11, synthesizing III-V family quantum point nucleus or II-III-V family cadmium-free alloy quantum point nucleus in the solution;
s12, adding a first anion precursor and a first cation precursor into the solution containing the quantum dot core, and coating a first inner shell layer outside the quantum dot core after reaction;
s13, adding a second anion precursor and a second cation precursor to the solution after the reaction of step S12, and coating a second inner shell layer on the first inner shell layer after the reaction.
It should be noted that, if the quantum dot core 101 is coated with more than two inner shell layers 102 in step S1, a step of coating the inner shell layers 102 is performed after step S13, and the specific coating method may refer to step S12 or S13.
In step S2, the first core-shell quantum dot, the third cation precursor, and the third anion precursor are mixed and reacted to obtain a product system containing the second core-shell quantum dot. In some embodiments, the ratio of the amount of species of cations in the third cation precursor to the amount of species of anions in the third anion precursor is (1:1) to (10: 1). It should be noted that, in step S2, the purified first core-shell quantum dots may be mixed with the third cation precursor and the third anion precursor, or the third cation precursor and the third anion precursor may be added to the solution after the reaction in step S13.
In step S3, the second core-shell quantum dot, the fourth cation precursor, and the fourth anion precursor are mixed and reacted to obtain a product system containing the core-shell quantum dot. In some embodiments, the ratio of the amount of species of cations in the fourth cation precursor to the amount of species of anions in the fourth anion precursor is (1:1) to (10: 1). It should be noted that, in step S3, the purified second core-shell quantum dots may be mixed with the fourth cation precursor and the fourth anion precursor, or the fourth cation precursor and the fourth anion precursor may be added to the solution after the reaction in step S2.
The first cation precursor, the second cation precursor, the third cation precursor, and the fourth cation precursor may each include a precursor of one kind of cation, or may each include a precursor of a plurality of kinds of cations. In some preferred embodiments, the first cation precursor, the second cation precursor, the third cation precursor, and the fourth cation precursor are zinc precursors.
The first anion precursor, the second anion precursor, the third anion precursor, and the fourth anion precursor may each include a precursor of one kind of anion, or may each include a precursor of a plurality of kinds of anions. It is worth mentioning that when the first cation precursor, the second cation precursor, the third cation precursor and the fourth cation precursor are the same, the forbidden bandwidth of each layer needs to be considered for selecting the first anion precursor, the second anion precursor, the third anion precursor and the fourth anion precursor, so as to satisfy that the forbidden bandwidth of each layer of material of the first core-shell quantum dot 100 is sequentially increased from inside to outside along the radial direction, the forbidden bandwidth of the material of the first outer shell 200 is smaller than that of the outermost layer of material of the first core-shell quantum dot 100, and the forbidden bandwidth of the material of the second outer shell 300 is larger than that of the outermost layer of material of the second core-shell quantum dot.
In some preferred embodiments, the first, second, third, and fourth anion precursors are each selected from selenium precursors or sulfur precursors. The selenium precursor can be, but is not limited to, Se-TOP (trioctylphosphine selenium), Se-TBP (tributylphosphine selenium), Se-ODE solution (octadecene-selenium), Se powder-ODE suspension, TMS-Se [ tris (trimethylsilylium) selenium ]; the sulfur precursor may be, but is not limited to, S-TOP (trioctylphosphine sulfur), S-TBP (tributylphosphine sulfur), S-ODE (octadecene-sulfur), alkyl mercaptan, TMS-S [ tris (trimethylsilyloxy) sulfur ].
According to the common knowledge in the field, the forbidden bandwidth of ZnS is larger than that of ZnSe, and the forbidden bandwidth of ZnSe is larger than that of InP.
In some embodiments, in step S11, after synthesizing the iii-v quantum dot core or the ii-iii-v cadmium-free alloy quantum dot core, a sulfur source is added to react for a period of time to obtain the quantum dot core with sulfur on the surface, wherein the sulfur source may be one or more selected from S-ODE (octadecene-sulfur solution), S-TBP (tributylphosphine sulfide), and S-TOP (trioctylphosphine sulfide). In the step S11, after the sulfur source is added, the sulfur source is modified to the surface of the quantum dot core through a chemical reaction, so that the surface of the quantum dot core or the inside of the quantum dot core has sulfur elements, or both the surface of the quantum dot core and the inside of the quantum dot core have sulfur elements, and the quantum dot core modified by the sulfur source is used to prepare the core-shell quantum dot, which is beneficial to narrowing the half-peak width of the core-shell quantum dot.
In some embodiments, step S11 is specifically: mixing an indium precursor and a solvent to form a mixed solution, or mixing the indium precursor, a zinc precursor and the solvent to form a mixed solution, adding a phosphorus precursor into the mixed solution at the temperature of between 30 and 60 ℃, heating to between 280 and 310 ℃, reacting for 30 to 120 seconds, then dropwise adding a sulfur source, and reacting for 5 to 15 minutes. Wherein the ratio of the amount of sulfur element in the sulfur source to the amount of indium element in the indium precursor is (1:3) to (1: 30).
Step S12 specifically includes: and (3) rapidly adding a selenium precursor into the solution reacted in the step S11 at 280-310 ℃, reacting for 5-15 min, then rapidly adding a zinc precursor, reacting for 5-15 min, then rapidly adding the selenium precursor, reacting for 5-15 min, finally rapidly adding the zinc precursor, and reacting for 5-15 min.
Step S13 specifically includes: and (3) adding a sulfur precursor into the solution reacted in the step S12 at the temperature of 280-310 ℃ for reaction for 5-15 min.
The application also provides a quantum dot composition which comprises the core-shell structure quantum dot. It will be understood by those skilled in the art that the quantum dot composition may be, but is not limited to, a quantum dot ink, a quantum dot film, and the like.
The application also provides a quantum dot device which comprises the core-shell structure quantum dot. It will be understood by those skilled in the art that the quantum dot device may be, but is not limited to, a quantum dot light emitting device, a quantum dot display device, a quantum dot solar cell, a photodetector, a bioprobe, and the like.
[ example 1 ]
Preparing a first core-shell quantum dot InZnP/ZnSe/ZnS:
(1) preparing quantum dot core InZnP: 0.3mmol of In (Ac) was weighed3、0.4mmol Zn(Ac)21.3mmol of MA (tetradecanoic acid) and 60mmol of ODE (octadecene) are put into a 100mL round-bottom flask, and the gas is exhausted for 2min at room temperature, and then the temperature is raised to 180 ℃ and the gas is exhausted for more than 30 min; cooling the system to about 35 ℃, injecting a mixed solution of 0.15mmol TMS-P and 0.7mL TOA (tri-n-octylamine), heating to 290 ℃ for reaction for 1min, slowly dropwise adding 0.3mL S-ODE (with the concentration of 0.1mol/L), and reacting for 10 min;
(2) preparation of InZnP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (with the concentration of 1mol/L) into the solution reacted in the step (1) and reacting for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(the concentration is 0.2mol/L), and the reaction is carried out for 10 min;
(3) preparation of InZnP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol OA (oleic acid) and 60mmol ODE in a 100mL round-bottom flask, exhausting gas for 2min at room temperature, heating to 180 ℃, exhausting gas for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributylphosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol, and purifying.
Preparing a third core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe/ZnS:
(5) weighing 7mmol Zn (Ac)214mmol of OA (oleic acid) and 47mmol of ODE are put in a 100mL round-bottom flask, the air is exhausted for 2min at room temperature, the temperature is increased to 180 ℃ and the air is exhausted for 30min, InZnP/ZnSe quantum dots in the step (4) are injected at 180 ℃, the temperature is increased to 305 ℃, 2.4mL of S-TBP (the concentration is 0.5mol/L) is injected rapidly, and the reaction is carried out for 60 min; then cooling and adding acetone and methanol for purification.
[ example 2 ]
Preparing a first core-shell quantum dot InZnP/ZnSe/ZnS:
(1) preparing quantum dot core InZnP: 0.3mmol of In (Ac) was weighed3、0.4mmol Zn(Ac)21.3mmol MA, 60mmol ODE (octadecene) to a 100mL round bottom flask, exhausting gas for 2min at room temperature, then heating to 180 ℃ and exhausting gas for more than 30 min; the temperature of the system is reduced to about 35 ℃, the mixed solution of 0.15mmol TMS-P and 0.7mL TOA (tri-n-octylamine) is injected, and then the temperature is increased to 290 ℃ for reaction for 10 min.
(2) Preparation of InZnP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (with the concentration of 1mol/L) into the solution reacted in the step (1) and reacting for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(the concentration is 0.2mol/L), and the reaction is carried out for 10 min;
(3) preparation of InZnP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)218mmol of OA (oleic acid) and 60mmol of ODEExhausting gas for 2min at room temperature in a 100mL round bottom flask, heating to 180 ℃ and exhausting gas for 30min, injecting InZnP/ZnSe/ZnS quantum dots obtained in the step (3) at 180 ℃, heating to 305 ℃ and quickly injecting 3mL Se-TBP (tributylphosphine selenium) (with the concentration of 0.5mol/L) for reaction for 120 min; cooling, adding acetone and methanol for purification.
Preparing a third core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe/ZnS:
(5) weighing 7mmol Zn (Ac)214mmol of OA (oleic acid) and 47mmol of ODE are put in a 100mL round-bottom flask, the air is exhausted for 2min at room temperature, the temperature is increased to 180 ℃ and the air is exhausted for 30min, InZnP (S)/ZnSe/ZnS/ZnSe quantum dots in the step (4) are injected at 180 ℃, the temperature is increased to 305 ℃, 2.4mL of S-TBP (the concentration is 0.5mol/L) is injected rapidly, and the reaction is carried out for 60 min; then cooling and adding acetone and methanol for purification.
[ example 3 ]
Preparing a first core-shell quantum dot InZnP/ZnSe/ZnS:
(1) preparing quantum dot core InZnP: 0.3mmol of In (Ac) was weighed3、0.4mmol Zn(Ac)21.3mmol MA and 60mmol ODE (octadecene) are put into a 100mL round-bottom flask, and then the gas is discharged for 2min at room temperature, and then the gas is discharged for more than 30min after the temperature is raised to 180 ℃; cooling the system to about 35 ℃, injecting a mixed solution of 0.15mmol TMS-P and 0.7mL TOA (tri-n-octylamine), heating to 290 ℃ for reaction for 1min, slowly dropwise adding 0.3mL S-ODE (with the concentration of 0.1mol/L), and reacting for 10 min;
(2) preparation of InZnP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (with the concentration of 1mol/L) into the solution reacted in the step (1) and reacting for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) for 10 min.
(3) Preparation of InZnP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)218mmol of OA (oleic acid) and 60mmol of ODE in 100mL round bottomExhausting gas for 2min at room temperature, heating to 180 ℃, exhausting gas for 30min, injecting InZnP/ZnSe/ZnS quantum dots obtained in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributylphosphine selenium) (with the concentration of 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol, and purifying.
[ example 4 ]
Preparing a first core-shell quantum dot InZnP/ZnSe/ZnS:
(1) preparing quantum dot core InZnP: 0.3mmol of In (Ac) was weighed3、0.4mmol Zn(Ac)21.3mmol MA and 60mmol ODE (octadecene) are put into a 100mL round-bottom flask, and then the gas is discharged for 2min at room temperature, and then the gas is discharged for more than 30min after the temperature is raised to 180 ℃; cooling the system to about 35 ℃, injecting a mixed solution of 0.15mmol TMS-P and 0.7mL TOA (tri-n-octylamine), and then heating to 290 ℃ for reaction for 10 min;
(2) preparation of InZnP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (with the concentration of 1mol/L) into the solution reacted in the step (1) and reacting for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(the concentration is 0.2mol/L), and the reaction is carried out for 10 min;
(3) preparation of InZnP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InZnP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol OA (oleic acid) and 60mmol ODE in a 100mL round-bottom flask, exhausting gas for 2min at room temperature, heating to 180 ℃, exhausting gas for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributylphosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol, and purifying.
[ example 5 ]
Preparing a first core-shell quantum dot InP/ZnSe/ZnS:
(1) preparing quantum dot core InP: 0.3mmol of In (Ac) was weighed30.81mmol MA and 60mmol ODE (octaene) to 100mL round bottom bakedExhausting air at room temperature for 2min, heating to 180 deg.C, and exhausting air for more than 30 min; cooling the system to about 35 ℃, injecting a mixed solution of 0.12mmol TMS-P and 0.7mL TOA (tri-n-octylamine), heating to 290 ℃ for reaction for 1min, slowly dropwise adding 0.3mL S-ODE (with the concentration of 0.1mol/L), and reacting for 10 min;
(2) preparation of InP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP concentration (1mol/L) into the solution reacted in the step (1) for reaction for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) and reacting for 10 min;
(3) preparation of InP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol OA (oleic acid) and 60mmol ODE in a 100mL round-bottom flask, exhausting gas for 2min at room temperature, heating to 180 ℃, exhausting gas for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributylphosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol, and purifying.
Preparing a third core-shell quantum dot InP/ZnSe/ZnS/ZnSe/ZnS:
(5) weighing 7mmol Zn (Ac)2Exhausting gas at room temperature for 2min, heating to 180 ℃ and exhausting gas for 30min, injecting InP/ZnSe/ZnS/ZnSe quantum dots obtained in the step (4) at 180 ℃, heating to 305 ℃, quickly injecting 2.4mL of S-TBP (with the concentration of 0.5mol/L) and reacting for 60min in a 100mL round-bottom flask; then cooling and adding acetone and methanol for purification.
[ example 6 ]
Preparing a first core-shell quantum dot InP/ZnSe/ZnS:
(1) preparing quantum dot core InP: 0.3mmol of In (Ac) was weighed30.81mmol MA and 60mmol ODE (octadecene) into a 100mL round bottom flask, degassing at room temperature for 2min, then heating to 180 deg.C and degassing for 3More than 0 min; the temperature of the system is reduced to about 35 ℃, the mixed solution of 0.12mmol TMS-P and 0.7mL TOA (tri-n-octylamine) is injected, and then the temperature is increased to 290 ℃ for reaction for 10 min.
(2) Preparation of InP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (with the concentration of 1mol/L) into the solution reacted in the step (1) and reacting for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(the concentration is 0.2mol/L), and the reaction is carried out for 10 min;
(3) preparation of InP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol of OA (oleic acid) and 60mmol of ODE in a 100ml round bottom flask, exhausting for 2min at room temperature, heating to 180 ℃, exhausting for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributyl phosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol for purification.
Preparing a third core-shell quantum dot InP/ZnSe/ZnS/ZnSe/ZnS:
(5) weighing 7mmol Zn (Ac)214mmol OA and 47mmol ODE are put in a 100mL round-bottom flask, the mixture is discharged for 2min at room temperature, the mixture is heated to 180 ℃ and discharged for 30min, InZnP (S)/ZnSe/ZnS/ZnSe quantum dots in the step (4) are injected at 180 ℃, the temperature is raised to 305 ℃, 2.4mL S-TBP (with the concentration of 0.5mol/L) is rapidly injected, and the reaction is carried out for 60 min. Cooling, adding acetone and methanol, and purifying.
[ example 7 ]
Preparing a first core-shell quantum dot InP/ZnSe/ZnS:
(1) preparing quantum dot core InP: weighing 0.3mmol of In (Ac)3, 0.81mmol of MA and 60mmol of ODE (octadecene) into a 100mL round-bottom flask, exhausting for 2min at room temperature, then heating to 180 ℃, and exhausting for more than 30 min; the temperature of the system is reduced to about 35 ℃, a mixed solution of 0.12mmol TMS-P and 0.7mL TOA (tri-n-octylamine) is injected, and then the temperature is increased to 290 ℃. Then heating to 290 ℃ to react for 1min, slowly dropwise adding 0.3ml of S-ODE (the concentration is 0.1mol/L) to react for 10 min;
(2) preparation of InP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (1mol/L) into the solution reacted in the step (1) for reaction for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) and reacting for 10 min;
(3) preparation of InP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol of OA (oleic acid) and 60mmol of ODE in a 100ml round bottom flask, exhausting for 2min at room temperature, heating to 180 ℃, exhausting for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributyl phosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol for purification.
[ example 8 ]
Preparing a first core-shell quantum dot InP/ZnSe/ZnS:
(1) preparing quantum dot core InP: weighing 0.3mmol of In (Ac)3, 0.81mmol of MA and 60mmol of ODE (octadecene) into a 100mL round-bottom flask, exhausting for 2min at room temperature, then heating to 180 ℃, and exhausting for more than 30 min; the temperature of the system is reduced to about 35 ℃, a mixed solution of 0.12mmol TMS-P and 0.7mL TOA (tri-n-octylamine) is injected, and then the temperature is increased to 290 ℃. Then the temperature is increased to 290 ℃ for reaction for 10 min.
(2) Preparation of InP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (1mol/L) into the solution reacted in the step (1) for reaction for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) and reacting for 10 min;
(3) preparation of InP/ZnSe/ZnS: dropwise adding 2mL of S-ODE (with the concentration of 0.1mol/L) into the solution reacted in the step (2) at 290 ℃, and reacting for 10 min; then cooling and adding acetone and methanol for purification.
Preparing a second core-shell quantum dot InP/ZnSe/ZnS/ZnSe:
(4) 9mmol of Zn (Ac)2Placing 18mmol of OA (oleic acid) and 60mmol of ODE in a 100ml round bottom flask, exhausting for 2min at room temperature, heating to 180 ℃, exhausting for 30min, injecting InZnP/ZnSe/ZnS quantum dots in the step (3) at 180 ℃, heating to 305 ℃, quickly injecting 3mLSe-TBP (tributyl phosphine selenium) (the concentration is 0.5mol/L), and reacting for 120 min; cooling, adding acetone and methanol for purification.
Comparative example 1
(1) Preparing quantum dot core InZnP: 0.3mmol of In (Ac) was weighed3、0.4mmol Zn(Ac)21.3mmol MA and 60mmol ODE (octadecene) are put into a 100mL round-bottom flask, and then the gas is discharged for 2min at room temperature, and then the gas is discharged for more than 30min after the temperature is raised to 180 ℃; the temperature of the system is reduced to about 35 ℃, the mixed solution of 0.15mmol TMS-P and 0.7mL TOA (tri-n-octylamine) is injected, and then the temperature is increased to 290 ℃ for reaction for 10 min.
(2) Preparation of InZnP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (1mol/L) into the solution reacted in the step (1) for reaction for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) and reacting for 10 min; cooling, adding acetone and methanol, and purifying.
(3) Preparation of InZnP/ZnSe/ZnS: weighing 7mmol Zn (Ac)2And 14mmol OA and 47mmol ODE are put in a 100mL round-bottom flask, the mixture is exhausted for 2min at room temperature, the temperature is increased to 180 ℃ and is exhausted for 30min, InZnP/ZnSe quantum dots in the step (3) are injected at 180 ℃, the temperature is increased to 305 ℃, 2.4mL S-TBP (the concentration is 0.5mol/L) is rapidly injected, and the reaction is carried out for 60 min. Cooling, adding acetone and methanol, and purifying.
Comparative example 2
(1) Preparing quantum dot core InP: 0.3mmol of In (Ac) was weighed30.81mmol MA and 60mmol ODE (octadecene) are put into a 100mL round-bottom flask, and the gas is exhausted for 2min at room temperature, and then the temperature is raised to 180 ℃ and the gas is exhausted for more than 30 min; cooling the system to about 35 deg.C, injecting into a container of 0.12And (3) mixing mmol TMS-P and 0.7mL TOA (tri-n-octylamine), and heating to 290 ℃ for reaction for 10 min.
(2) Preparation of InP/ZnSe: at 290 ℃, quickly injecting 0.1mL of Se-TOP (1mol/L) into the solution reacted in the step (1) for reaction for 10 min; then rapidly injecting 5mL of Zn (OA)2(concentration 0.2mol/L) and reacting for 10 min; then quickly injecting 0.1mL of Se-TOP (the concentration is 1mol/L) to react for 10 min; finally, 5mL Zn (OA) is injected rapidly2(concentration 0.2mol/L) and reacting for 10 min; cooling, adding acetone and methanol, and purifying.
(3) Preparation of InP/ZnSe/ZnS: weighing 7mmol Zn (Ac)2And 14mmol OA and 47mmol ODE are put in a 100mL round-bottom flask, the mixture is exhausted for 2min at room temperature, the temperature is increased to 180 ℃ and is exhausted for 30min, InZnP/ZnSe quantum dots in the step (2) are injected at 180 ℃, the temperature is increased to 305 ℃, 2.4mL S-TBP (the concentration is 0.5mol/L) is rapidly injected, and the reaction is carried out for 60 min. Cooling, adding acetone and methanol, and purifying.
The fluorescence emission spectrum instrument is adopted to test the fluorescence emission peak and half-peak width of the nuclear shell quantum dot, and the detection method of the quantum efficiency of the solution quantum dot comprises the following steps: a450 nm blue LED lamp is used as a light source, an integrating sphere is used for respectively testing the spectrum of the blue light source and the spectrum after the quantum dot solution passes through, and the quantum dot light efficiency is calculated by using the integral area of the spectrum. Quantum efficiency ═ 100% for (peak area of quantum dot emission)/(peak area of blue light source-peak area of blue light not absorbed after transmission through quantum dot solution). The test results are shown in Table 1.
Table 1 lists the fluorescence absorption peak position, half-peak width, and quantum efficiency of the core-shell quantum dots of each example and comparative example 1. As can be seen from the data in table 1, treatment of the quantum dot core with a sulfur source is beneficial in narrowing the half-peak width. The quantum efficiency of the core-shell quantum dot of example 2 is higher than that of the core-shell quantum dot of comparative example 1, which shows that the quantum efficiency of the core-shell quantum dot can be significantly improved by sequentially coating a ZnSe shell layer and ZnS outside the ZnS shell layer.
TABLE 1
| Core-shell quantum dot structure | PL/nm | Half peak width/nm | Quantum efficiency/%) | |
| Comparative example 1 | InZnP/ZnSe/ZnS | 533 | 38 | 53.2％ |
| Comparative example 2 | InP/ZnSe/ZnS | 531 | 38 | 51.8％ |
| Example 1 | InZnP (sulfur source processing)/ZnSe/ZnS | 532 | 35 | 68.5％ |
| Example 2 | InZnP/ZnSe/ZnS/ZnSe/ZnS | 532 | 36 | 66.8％ |
| Example 3 | InZnP (sulfur source processing)/ZnSe/ZnS/ZnSe | 534 | 36 | 60.5％ |
| Example 4 | InZnP/ZnSe/ZnS/ZnSe | 533 | 38 | 59.5％ |
| Example 5 | InP (sulfur source treatment)/ZnSe/ZnS | 530 | 36 | 64.8％ |
| Example 6 | InP/ZnSe/ZnS/ZnSe/ZnS | 530 | 36.5 | 62.3％ |
| Example 7 | InP (sulfur source treatment)/ZnSe/ZnS/ZnSe | 532 | 36.5 | 58.0％ |
| Example 8 | InP/ZnSe/ZnS/ZnSe | 632 | 38 | 57.8％ |
The quantum dots of the example 1 and the quantum dots of the comparative example 1 are respectively used for manufacturing quantum dot diaphragms, the preparation methods of the diaphragms are the same, and the steps are as follows: and mixing the quantum dots with polyacrylate glue (wherein the quantum dots account for 3 wt%), coating the mixture on one barrier film, covering the other barrier film after the coating is finished, and carrying out ultraviolet curing. The resulting film was subjected to various conditions and subjected to various time-dependent color coordinates (according to the 1931CIE-XYZ standard color system). The test conditions included 70 ℃ illumination, 65 ℃ and 95% relative humidity, 85 ℃, 65 ℃, color point results are shown in tables 2 and 4.
Table 2 shows the color point variation of InZnP (sulfur source treated)/ZnSe/ZnS/ZnSe/ZnS quantum dots of example 1 under different aging conditions (70 ℃ illumination, 65 ℃/95% relative humidity, 85 ℃, 65 ℃). Table 3 shows the percentage change in color point in color coordinates for InZnP (sulfur source treated)/ZnSe/ZnS quantum dots of example 1 under different aging conditions.
TABLE 2
TABLE 3
Table 4 shows the color point change under different aging conditions for InZnP/ZnSe/ZnS of comparative example 1, and Table 5 shows the color point change percentage under different aging conditions for InZnP/ZnSe/ZnS of comparative example 1.
TABLE 4
TABLE 5
As can be seen from tables 2, 3, 4, 5: the color point change of the example 1 is obviously smaller than that of the comparative example 1 under the condition of illumination at 70 ℃, which shows that the high-temperature illumination stability of the quantum dots of the example 1 is obviously better than that of the comparative example 1.
The foregoing has described the general principles, essential features, and advantages of the application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, which are intended as illustrations of the principles of the application, and that various changes and modifications can be made without departing from the spirit and scope of the application, and the scope of the application is to be protected. The scope of protection claimed by this application is defined by the following claims and their equivalents.
Claims (14)
1. The quantum dot with the core-shell structure is characterized by comprising:
the first core-shell quantum dot comprises a quantum dot core and at least two inner shell layers coated outside the quantum dot core, and the forbidden bandwidth of each layer of material of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction; and
and the first outer shell layer is directly coated outside the first core-shell quantum dot, and the forbidden band width of the first outer shell layer material is smaller than that of the inner shell layer material on the outermost layer of the first core-shell quantum dot.
2. The core-shell quantum dot according to claim 1, further comprising a second outer shell layer directly coated outside the first outer shell layer, wherein a forbidden bandwidth of the second outer shell layer material is greater than that of the first outer shell layer material.
3. The quantum dot with the core-shell structure as claimed in claim 1, wherein the quantum dot with the core-shell structure is a cadmium-free quantum dot, the quantum dot core is selected from one of group iii-v quantum dots or group ii-iii-v alloy quantum dots, and the material of each inner shell layer is selected from one of group ii-vi semiconductor materials.
4. The quantum dot with the core-shell structure as claimed in claim 1, wherein the first core-shell quantum dot has a structure of InZnP/ZnSe/ZnS or InP/ZnSe/ZnS, and the first shell layer is made of ZnSe.
5. The quantum dot with the core-shell structure according to claim 4, further comprising a second outer shell layer directly coated outside the first outer shell layer, wherein the second outer shell layer is made of ZnS.
6. The core-shell quantum dot according to any of claims 1 to 5, wherein the quantum dot core comprises elemental sulfur.
7. The preparation method of the core-shell structure quantum dot is characterized by comprising the following steps:
s1, synthesizing a quantum dot core, coating at least two inner shell layers outside the quantum dot core to obtain a first core-shell quantum dot,
the forbidden bandwidth of each layer of material of the first core-shell quantum dot is sequentially increased from inside to outside along the radial direction;
and S2, coating a first outer shell layer outside the first core-shell quantum dot to obtain a second core-shell quantum dot, wherein the forbidden bandwidth of the first outer shell layer material is less than that of the inner shell layer material on the outermost layer of the first core-shell quantum dot.
8. The method for preparing the core-shell quantum dot according to claim 7, wherein after the step S2, the method further comprises: step S3, a second shell layer is coated outside the second core-shell quantum dot, and a forbidden bandwidth of the second shell layer material is greater than a forbidden bandwidth of the outermost layer material of the second core-shell quantum dot.
9. The method for preparing the quantum dot with the core-shell structure according to claim 8,
the step S1 includes the steps of:
s11, synthesizing III-V family quantum point nucleus or II-III-V family cadmium-free alloy quantum point nucleus in the solution;
s12, adding a first anion precursor and a first cation precursor to the solution containing the quantum dot core, and coating a first layer of the inner shell layer outside the quantum dot core after reaction;
s13, adding a second anion precursor and a second cation precursor into the solution after the reaction of the step S12, and coating a second inner shell layer on the first inner shell layer after the reaction; alternatively, adding a second anion precursor to the solution after the reaction of the step S12, the second anion precursor reacting with the first cation precursor unreacted in the step S12, thereby coating a second layer of the inner shell layer on the first layer of the inner shell layer;
in the step S2, the first core-shell quantum dot, the third cation precursor, and the third anion precursor are mixed and reacted to obtain a product system containing the second core-shell quantum dot;
in the step S3, the second core-shell quantum dot, the fourth cation precursor, and the fourth anion precursor are mixed and reacted to obtain a product system containing the core-shell quantum dot.
10. The method for preparing the quantum dot with the core-shell structure according to claim 9, wherein in the step S11, after the group iii-v quantum dot core or the group ii-iii-v cadmium-free alloy quantum dot core is synthesized, a sulfur source is added to react for a period of time to obtain the quantum dot core with sulfur on the surface, preferably, the sulfur source is selected from one or more of S-ODE, S-TBP and S-TOP.
11. The method for preparing a quantum dot with a core-shell structure according to claim 10, wherein the ratio of the amount of sulfur in the sulfur source to the amount of indium in the indium precursor is (1:3) to (1: 30).
12. The method for preparing quantum dots with core-shell structures according to any one of claims 9 to 11, wherein the first cation precursor, the second cation precursor, the third cation precursor and the fourth cation precursor are zinc precursors, and the first anion precursor, the second anion precursor, the third anion precursor and the fourth anion precursor are respectively selected from selenium precursors or sulfur precursors.
13. A quantum dot composition comprising the core-shell quantum dot according to any one of claims 1 to 6, or the core-shell quantum dot prepared by the method according to any one of claims 7 to 12.
14. The quantum dot device is characterized by comprising the core-shell structure quantum dot as claimed in any one of claims 1 to 6, or the core-shell structure quantum dot prepared by the method as claimed in any one of claims 7 to 12.
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| EP4219653A1 (en) * | 2022-01-26 | 2023-08-02 | Samsung Electronics Co., Ltd. | Semiconductor nanoparticle, production method thereof, and electroluminescent device and display device including the same |
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