CN113956882A - Core-shell structure quantum dot, preparation method thereof and display device comprising core-shell structure quantum dot - Google Patents

Core-shell structure quantum dot, preparation method thereof and display device comprising core-shell structure quantum dot Download PDF

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CN113956882A
CN113956882A CN202011466975.5A CN202011466975A CN113956882A CN 113956882 A CN113956882 A CN 113956882A CN 202011466975 A CN202011466975 A CN 202011466975A CN 113956882 A CN113956882 A CN 113956882A
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quantum dot
shell
shell structure
shell layer
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曹越峰
单玉亮
曹佳佳
杨涵妮
乔登清
张思源
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Suzhou Xingshuo Nanotech Co Ltd
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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

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Abstract

The application provides a core-shell structure quantum dot, a preparation method thereof and a display device comprising the same, wherein the core-shell structure quantum dot comprises a core body and a light absorption shell layer, and the light absorption shell layer is a compound containing indium and selenium; the quantum dot with the core-shell structure can effectively enhance the blue light absorbance, improve the quantum efficiency of the quantum dot with the core-shell structure and reduce the low half-peak width.

Description

Core-shell structure quantum dot, preparation method thereof and display device comprising core-shell structure quantum dot
Technical Field
The application belongs to the technical field of quantum dots, and particularly relates to a core-shell structure quantum dot, a preparation method thereof and a display device comprising the core-shell structure quantum dot.
Background
Quantum dots (also called semiconductor nanocrystals) are a new type of semiconductor nanomaterial with a size of 1-10 nm. They have unique Photoluminescent (PL) and Electroluminescent (EL) properties due to quantum size effects and dielectric confinement effects. Compared with the traditional organic fluorescent dye, the quantum dot has excellent optical characteristics of high quantum yield, high photochemical stability, difficult photolysis, wide excitation, narrow emission, high color purity, adjustable luminous color through controlling the size of the quantum dot and the like, and has wide application prospect in the technical field of display.
At present, cadmium quantum dots have the advantages of high quantum efficiency, small half-peak width, strong blue light absorption and good stability, and have gradually begun to be commercialized, but due to the existence of heavy metal element cadmium, the cadmium-free quantum dots do not meet the increasingly important environmental protection requirements, so the development of novel cadmium-free quantum dots is very urgent. However, compared with the commonly used cadmium quantum dots, InP in the prior art has many disadvantages such as poor blue light absorption, large half-peak width, and poor stability, which limits the application thereof. Therefore, there is a need to optimize the synthesis of cadmium-free quantum dots to improve the blue light absorption performance, so as to promote the commercialization of the quantum dots.
Disclosure of Invention
In view of the above technical problems, the present application provides a core-shell structure quantum dot, which includes a core body and a light absorption shell layer, wherein the light absorption shell layer is a compound containing indium and selenium.
Further, the light absorption shell layer is In2SexS3-xWherein, 0<x≤3。
Further, the weight percentage of the light absorption shell layer in the core-shell structure quantum dot is 10-99%, and preferably 10-30%.
The light absorption shell further comprises a first shell layer, and the first shell layer is coated on the outer surface of the light absorption shell layer; or the first shell layer is positioned between the core body and the light-absorbing shell layer and covers the outer surface of the core body;
preferably, the first shell layer comprises ZnS1-ySeyWherein y is more than or equal to 0 and less than or equal to 1.
Further, a second shell layer is included outside the light absorbing shell layer and the first shell layer, the second shell layer comprising ZnS1-zSezWherein z is more than or equal to 0 and less than or equal to 1.
Further, when the emission peak wavelength is at 510-540nm, the OD450 of the core-shell structure quantum dot is greater than 0.3mg/(mL cm); when the emission peak wavelength is 610-640nm, the OD450 of the quantum dot with the core-shell structure is more than 0.6 mg/(mL-cm).
The application also provides a preparation method of the core-shell structure quantum dot, which comprises the following steps:
s1, providing a core body or an initial quantum dot, wherein the initial quantum dot comprises the core body and a first shell layer coated on the outer surface of the core body;
s2, mixing an indium precursor with the core body or the initial quantum dot, and adding a selenium precursor or a selenium precursor and a sulfur precursor at 140-320 ℃ to form a light absorption shell layer on the core body or the initial quantum dot, wherein the light absorption shell layer is a compound containing indium element and selenium element.
Further, after the step S2, the method further includes the steps of:
s3, adding a second shell layer precursor at 240-340 ℃ to form a second shell layer on the light absorption shell layer.
Further, the indium precursor includes an organic indium.
The application also comprises a display device which comprises the core-shell structure quantum dot or the core-shell structure quantum dot prepared by the method.
Has the advantages that:
(1) the quantum dot with the core-shell structure comprises a core body and a light absorption shell layer, wherein the light absorption shell layer is a compound containing indium and selenium, so that the quantum dot with the core-shell structure, which is small in half-peak width and high in OD450, can be obtained more easily.
(2) According to the preparation method of the core-shell structure quantum dot, organic indium is used as an indium precursor, the activity is high, and the organic indium is more likely to react with elemental selenium or elemental selenium and elemental sulfur to obtain a light absorption shell layer, so that the core-shell structure quantum dot is more excellent in performance, lower in preparation cost and higher in production efficiency, and is suitable for industrial production.
(3) Compared with the prior art, the color film and the display device prepared by the quantum dots with the core-shell structures have the advantages that the light conversion efficiency is remarkably improved, and the light emitting performance is more excellent.
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FIG. 1 is a graph comparing absorption spectra of core-shell structured quantum dots of example 1 and comparative example 1 of the present application;
fig. 2 is an emission spectrum of the core-shell structure quantum dot of embodiment 1 of the present application;
fig. 3 is a TEM image of the core-shell structure quantum dot according to example 1 of the present application.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments. Unless otherwise defined, all terms (including technical and scientific terms) in the specification may be defined as commonly understood by one of ordinary skill in the art. Unless clearly defined, terms defined in a general dictionary may be undesirably or exaggeratedly explained. Furthermore, unless explicitly described to the contrary, the word "comprise" and variations such as "comprises" or "comprising" will be understood to imply the inclusion of stated elements (elements) but not the exclusion of any other elements (elements).
In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. Like reference numerals refer to like elements throughout the specification.
It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly 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.
Furthermore, the singular includes the plural unless otherwise mentioned. As used herein, at least one of the terms "a", "an", "the" and "… …" do not denote a limitation of quantity, but are intended to include both the singular and the plural, unless the context clearly indicates otherwise. For example, "an element" has the same meaning as "at least one element" unless the context clearly dictates otherwise. "at least one" is not to be construed as limiting "a" or "an". "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprises" and/or "comprising," or variations thereof, when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
It will be understood that, although the terms "first," "second," "third," etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section.
As described in the background art, the indium phosphide core-shell structure quantum dot in the prior art has a larger difference in performance than the cadmium-based core-shell structure quantum dot, such as a large half-peak width, a weak blue light absorption, and a low quantum yield. Based on the core-shell structure quantum dot, the core-shell structure quantum dot comprises a core body and a light absorption shell layer coated on the core body, wherein the light absorption shell layer contains In2SexS3-xWherein, 0<x is less than or equal to 3. The inventor finds that the light absorption shell layer is a compound containing indium element and selenium element, so that the core-shell structure quantum dot has a high absorption value at 450nm, and the light conversion efficiency of the core-shell structure quantum dot photoluminescence film prepared from the core-shell structure quantum dot is improved.
It can be understood that the excitation light currently used for exciting the core-shell structure quantum dots in the photoluminescence application is mostly blue light with a wavelength of 450nm, and in the application, the absorption value of the core-shell structure quantum dots with a certain concentration at 450nm in a UV absorption spectrum is defined as OD450, which represents the absorption capacity of the core-shell structure quantum dots to the blue light with a wavelength of 450 nm.
In a specific embodiment of the present application, the light absorbing shell layer includes at least one of an indium selenide compound and an indium selenide sulfide compound, so that the OD450 of the quantum dot having the core-shell structure is significantly increased. The light-absorbing shell layer preferably comprises an indium selenide compound, so that the core-shell structure quantum dot obtains a more excellent OD 450.
In preferred embodiments, the core body comprises a group III-VI compound effective to increase the OD450 of the core-shell structured quantum dot.
More preferably, the core body contains InP, the lattice parameter matching of the core body and a light absorption shell layer of the compound containing indium element and selenium element is better, the shell layer grows more uniformly, the half-peak width of the core-shell structure quantum dot is reduced, and meanwhile, the OD450 of the core-shell structure quantum dot is obviously improved.
In a specific embodiment, the light absorption shell layer is 10-99% by weight in the core-shell structure quantum dot, so that the OD450 of the core-shell structure quantum dot is further improved, and the light absorption shell layer is preferably 10-30% by weight; further, the light absorption shell layer accounts for 50-70% of the quantum dot with the core-shell structure by weight, so that the quantum dot with the core-shell structure can obtain a high OD450 and maintain high quantum efficiency.
In a preferred embodiment, the thickness of the light absorption shell layer is 1-3 nm, so as to ensure that the quantum dot with the core-shell structure has a high OD 450.
In another specific embodiment of the present application, the quantum dot with the core-shell structure further includes a first shell layer, and the first shell layer is coated on the light-absorbing shell layer; or the first shell layer is positioned between the core body and the light-absorbing shell layer and coated on the core body; thereby leading the quantum dots with the core-shell structure to obtain better quantum efficiency.
In a preferred embodiment, the first shell layer comprises ZnS1-ySeyWherein y is more than or equal to 0 and less than or equal to 1, and is matched with the lattice parameter of the light absorption shell layerThe performance is good, so that the shell layer can uniformly grow on the core body or the light absorption shell layer, and the half-peak width of the quantum dot with the core-shell structure is further reduced.
In another embodiment of the present application, the quantum dot with the core-shell structure further includes a second shell layer outside the light-absorbing shell layer and the first shell layer, the second shell layer including ZnS1-zSezWherein z is more than or equal to 0 and less than or equal to 1 so as to improve the stability of the core-shell structure quantum dot.
In yet another embodiment of the present application, the OD450 of the core-shell structure quantum dot is greater than 0.3mg/(mL _ cm) when the emission peak wavelength is 510-540nm, and the OD450 of the core-shell structure quantum dot is greater than 0.6mg/(mL _ cm) when the emission peak wavelength is 610-640 nm.
The application also provides a preparation method of the core-shell structure quantum dot, which comprises the following steps:
s1, providing a core body or an initial quantum dot, wherein the initial quantum dot comprises the core body and a first shell layer coated on the outer surface of the core body;
the core body and the first shell layer may be prepared by a conventional method in the art, which is not limited in the present application.
S2, mixing an indium precursor with the core body or the initial quantum dot, and adding a selenium precursor or a selenium precursor and a sulfur precursor at 140-320 ℃ to form a light absorption shell layer on the core body or the initial quantum dot, wherein the light absorption shell layer is a compound containing indium element and selenium element.
A light absorption shell layer of a compound containing indium element and selenium element is coated on the core body, so that the OD450 of the quantum dot with the core-shell structure can be obviously improved.
In a specific embodiment of the present application, the reaction temperature in step S2 is preferably 160 to 240 ℃, so that the indium precursor and the selenium precursor or the selenium precursor and the sulfur precursor fully react, that is, the indium precursor can react with the selenium precursor, and the indium precursor can also react with the selenium precursor and the sulfur precursor together to form a light-absorbing shell layer with uniform thickness, thereby significantly improving the blue light absorbance of the core-shell quantum dot and reducing the half-peak width.
In another embodiment herein, the indium precursor herein comprises at least one of an indium fatty acid, an organic indium; the indium precursor has wide sources and can be selected according to requirements, wherein the organic indium has high activity, and a thicker light absorption shell layer is easy to form by using the organic indium precursor as the indium precursor, so that higher OD450 is obtained.
In a more preferable embodiment, the molar ratio of the organic indium to the selenium precursor or the selenium precursor to the sulfur precursor is 1 (1-5), so as to obtain a light absorption shell layer with a proper weight percentage content in the core-shell structure quantum dot, and thus the OD450 of the core-shell structure quantum dot is better.
In a preferred embodiment, the organo indium comprises at least one of triethylindium and trimethylindium, which readily react with the selenium precursor or with the selenium precursor and the sulfur precursor to form a compound comprising elemental indium and elemental selenium. The organic indium may be pure or dissolved in a nonpolar solvent to form a solution, and the molar concentration of the solution is, for example, 0.1 to 2M.
The selenium precursor and the sulfur precursor of the present application may further include a coordinating solvent or a non-coordinating solvent, so that they can be sufficiently efficiently reacted with the indium precursor to obtain an indium selenide compound or an indium selenide sulfide compound.
In another embodiment of the present application, the method for preparing the core-shell quantum dot further includes a step S3 of adding a second shell precursor at 240-340 ℃ to form a second shell layer on the light-absorbing shell layer, where the first shell layer may include ZnS1- ySeyWherein y is more than or equal to 0 and less than or equal to 1, the temperature for forming the first shell layer through reaction is 180-320 ℃, and the quantum efficiency of the core-shell structure quantum dot is effectively improved.
In another embodiment of the present application, the method for preparing the core-shell quantum dot may further include forming a second shell layer outside the light-absorbing shell layer and the first shell layer, the second shell layer including ZnS1-zSezAnd z is more than or equal to 0 and less than or equal to 1, the temperature for forming the second shell layer through reaction is 240-340 ℃, the thickness of the obtained second shell layer is uniform, and the stability of the core-shell structure quantum dot is improved.
The core-shell structure quantum dot prepared by the synthesis method can be added with an organic ligand, an organic solvent or a combination of the organic ligand and the organic solvent in each step, and the organic ligand can be combined to the surface of the quantum dot. The organic ligand includes but is not limited to at least one of oleylamine, oleic acid, C6-C18 alkyl thiol, triphenylphosphine oxide, mercapto polyethylene glycol fatty acid ester, mercapto polypropylene glycol fatty acid ester, mercapto polyglycerol fatty acid ester, mercapto-polyoxyethylene (20) sorbitan monolaurate, mercapto-polyoxyethylene (20) sorbitan stearate, mercapto-polyoxyethylene (20) sorbitan oleate, mercapto-polyoxyethylene (20) sorbitan palmitate, mercapto-sorbitan fatty acid ester, and the organic ligand may be a mixture of carboxylic acid and amine; organic solvents include, but are not limited to, C6 to C22 primary amines, such as hexadecylamine; secondary C6 to C22 amines, such as dioctylamine; c6 to C40 tertiary amines, such as trioctylamine; nitrogen-containing heterocyclic compounds such as pyridine; c6 to C40 aliphatic hydrocarbons (e.g., alkanes, alkenes, alkynes, etc.), such as hexadecane, octadecane, octadecene, or squalane; c6 to C30 aromatic hydrocarbons such as phenyl dodecane, phenyl tetradecane or phenyl hexadecane; phosphines substituted with C6 to C22 alkyl groups, such as trioctylphosphine; phosphine oxides substituted with C6 to C22 alkyl groups, such as trioctylphosphine oxide; c12 to C22 aromatic ethers such as phenyl ether or benzyl ether; or a combination thereof. At any step of the preparation of the core-shell structure quantum dot, the organic ligand, the organic solvent, and the required amount are appropriately selected.
The application also provides a display device which comprises the core-shell structure quantum dot. The display device of the present application includes, but is not limited to, any product or component having a display function, such as electronic paper, a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator, a vehicle-mounted display, an AR display, a VR display, and the like, and is particularly suitable for a color display device, and in some cases, the display device further includes a quantum dot film. The display device is prepared from the core-shell structure quantum dots, and is excellent in light emitting performance.
The display device may include a structure known to those skilled in the art of the present invention in addition to the core-shell structure quantum dot film, that is, the present invention includes a display device to which the core-shell structure quantum dot film of the present invention can be applied.
Core-shell structure quantum dot compositions, display devices, according to some exemplary embodiments of the present application are described in more detail below; however, the exemplary embodiments of the present application are not limited thereto.
Example 1
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing for 30 minutes at 120 ℃, converting into argon, heating to 180 ℃, adding 10mL of oleylamine solution containing 0.2M triethylindium, dropwise adding TOP-Se 2mL/h, and finishing dropwise adding for 30 minutes. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se for 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S for 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h for 120 minutes, cooling, and purifying to obtain InP/In2Se3the/ZnSe/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 13% by weight.
Example 2 (increasing amount of triethylindium)
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing for 30 minutes at 120 ℃, converting into argon, heating to 180 ℃, adding 20mL of oleylamine solution containing 0.2M triethylindium, dropwise adding TOP-Se for 4mL/h, and finishing dropwise adding for 30 minutes. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h for 120 minutes, cooling, and purifying to obtain InP/In2Se3the/ZnSe/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 26% by weight.
Example 3 (replacement by trimethylindium)
Taking 0.5g of green InP quantum dot core, adding into 20mL of oilVacuumizing at 120 ℃ for 30 minutes in amine, converting into argon, heating to 180 ℃, adding 10mL of oleylamine solution containing 0.2M trimethylindium, dropwise adding TOP-Se at 4mL/h for 30 minutes, and finishing dropwise adding. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h, after 120 minutes of dropwise addition, cooling, and purifying to obtain InP/In2Se3the/ZnSe/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 13% by weight.
Example 4 (exchange InSeS)
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing for 30 minutes at 120 ℃, converting into argon, heating to 180 ℃, adding 10mL of oleylamine solution containing 0.2M triethylindium, dropwise adding TOP-Se at the speed of 1mL/h, dropwise adding TOP-S at the speed of 1mL/h, and finishing dropwise adding for 30 minutes. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h, after 120 minutes of dropwise addition, cooling, and purifying to obtain InP/In2SexS3-xthe/ZnSe/ZnS core-shell structure quantum dot is 0<x≤3，In2SexS3-xThe content of (B) is 12% by weight.
Example 5 (increasing reaction temperature of InSe step)
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing for 30 minutes at 120 ℃, converting into argon, heating to 240 ℃, adding 10mL of oleylamine solution containing 0.2M triethylindium, dropwise adding TOP-Se 2mL/h, and finishing dropwise adding for 30 minutes. Keeping the temperature at 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se 4mL/h for 60 minutes, heating to 320 ℃, and adding 20mL of octadecylene solution containing 0.4M zinc stearate0.4M octadecene solution of zinc stearate, and dropwise adding TOP-S (total of 4 mL/h) for 60 minutes. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h for 120 minutes, cooling, and purifying to obtain InP/In2Se3the/ZnSe/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 15% by weight.
Example 6 (addition of first Shell ZnSe)
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing at 120 ℃ for 30 minutes, converting into argon, heating to 180 ℃, adding 2mL of octadecene solution containing 1M diethyl zinc, dropwise adding TOP-Se 2mL/h after 30 minutes of dropwise addition, adding 10mL of oleylamine solution containing 0.2M triethyl indium 10mL after 30 minutes of dropwise addition, dropwise adding TOP-Se 2mL/h, and completing 30 minutes of dropwise addition. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h for 120 minutes, cooling, and purifying to obtain InP/ZnSe/In2Se3/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 16% by weight.
Example 7 (addition of first Shell ZnSeS)
Taking 0.5g of green InP quantum dot core, adding the green InP quantum dot core into 20mL of oleylamine, vacuumizing at 120 ℃ for 30 minutes, converting into argon, heating to 180 ℃, adding 2mL of octadecene solution containing 1M diethyl zinc, dropwise adding TOP-Se, 1mL/h, TOP-S, 1mL/h, after 30 minutes of dropwise addition, adding 10mL of oleylamine solution containing 0.2M triethyl indium, dropwise adding TOP-Se, 2mL/h, and after 30 minutes of dropwise addition, completing the dropwise addition. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 deg.C, adding 40mL octadecene solution containing 0.4M zinc stearate, adding dropwise dodecyl mercaptan, 4mL/h, after dropping for 120 minutes, cooling and purifying to obtain InP/ZnSeS/In2Se3/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 18% by weight.
Example 8 (Replacing into Red Quantum dots)
Taking 0.5g of red InP quantum dot core, adding the red InP quantum dot core into 20mL of oleylamine, vacuumizing for 30 minutes at 120 ℃, converting into argon, heating to 180 ℃, adding 10mL of oleylamine solution containing 0.2M triethylindium, dropwise adding TOP-Se 2mL/h, and finishing dropwise adding for 30 minutes. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. Cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan at a rate of 4mL/h for 120 minutes, cooling, and purifying to obtain InP/ZnSe/In2Se3/ZnS core-shell structure quantum dot, wherein, In2Se3The content of (B) is 20% by weight.
Comparative example 1
Taking 0.5g of green InP quantum dot core, adding into 20mL of oleylamine, vacuumizing at 120 ℃ for 30 minutes, and converting into argon. Heating to 240 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-Se at a rate of 4mL/h after 60 minutes of dropwise addition, heating to 320 ℃, adding 20mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding TOP-S at a rate of 4mL/h after 60 minutes of dropwise addition. And cooling to 240 ℃, adding 40mL of octadecylene solution containing 0.4M zinc stearate, dropwise adding dodecyl mercaptan in a volume of 4mL/h for 120 minutes, and cooling and purifying to obtain the InP/ZnSe/ZnS core-shell structure quantum dot.
In the examples and the comparative examples of the application, a PerkinElmer Lambda 650 spectrophotometer is used for measuring the ultraviolet absorbance of the core-shell structure quantum dots, a hatichi F4500 fluorescence spectrophotometer is used for obtaining the fluorescence emission and absorption spectra of the core-shell structure quantum dots, a Tecnai G2F 20 transmission electron microscope is used for carrying out TEM representation on the core-shell structure quantum dots, the absorption spectra of the core-shell structure quantum dots of the examples 1 and the comparative examples 1 are shown in FIG. 1, the emission spectra of the core-shell structure quantum dots of the examples 1 are shown in FIG. 2, the TEM is shown in FIG. 3, in the TEM image, the light-colored part 11 is a dispersion liquid, and the dark-colored part 12 is the core-shell structure quantum dots.
The weight content of the light absorption shell layer in the core-shell structure quantum dots of examples 1 to 8 and comparative example 1, the emission peak wavelength, half-peak width and OD450 of the core-shell structure quantum dots were measured, and the quantum efficiency of the core-shell structure quantum dots was measured at the same time, with specific results as in table 1.
TABLE 1 optical Property parameter tables for core-shell structured Quantum dots in examples 1-8 and comparative example 1
Numbering Wavelength, nm Half peak width, nm Quantum efficiency% OD450，mg/(mL*cm)
Example 1 525 34 72 0.32
Example 2 527 34 64 0.35
Example 3 525 35 70 0.32
Example 4 523 37 74 0.30
Example 5 530 36 68 0.34
Example 6 523 33 78 0.30
Example 7 522 35 80 0.29
Example 8 625 45 78 0.94
Comparative example 1 520 38 75 0.15
As can be seen from the above table, OD450 of the core-shell structure quantum dots of examples 1 to 8 is significantly reduced compared to comparative example 1, and the core-shell structure quantum dots of the present application are formed by coating a core body with InSexS1-xThe light absorption shell layer can effectively improve the light absorption value of the quantum dot with the core-shell structure at 450nm, so that the light conversion efficiency of the prepared quantum dot color film and the prepared display device is improved, and the service life is prolonged.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.

Claims (10)

1. The quantum dot with the core-shell structure is characterized by comprising a core body and a light absorption shell layer, wherein the light absorption shell layer is a compound containing indium and selenium.
2. The core-shell quantum dot of claim 1, wherein the light absorbing shell layer is In2SexS3-xWherein, 0<x≤3。
3. The core-shell quantum dot according to claim 1, wherein the light absorption shell layer accounts for 10-99 wt% of the core-shell quantum dot.
4. The quantum dot with the core-shell structure as claimed in claim 1, further comprising a first shell layer located between the core body and the light-absorbing shell layer and coated on the outer surface of the core body;
preferably, the first shell layer comprises ZnS1-ySeyWherein y is more than or equal to 0 and less than or equal to 1.
5. The core-shell quantum dot according to any of claims 1 to 4, further comprising a second shell layer located outside the light-absorbing shell layer, wherein the second shell layer comprises ZnS1-zSezWherein z is more than or equal to 0 and less than or equal to 1.
6. The core-shell structure quantum dot according to any of claims 1-4, wherein the OD450 of the core-shell structure quantum dot is greater than 0.3mg/(mL cm) when the emission peak wavelength is at 510-540 nm; when the emission peak wavelength is 610-640nm, the OD450 of the quantum dot with the core-shell structure is more than 0.6 mg/(mL-cm).
7. A preparation method of a core-shell structure quantum dot is characterized by comprising the following steps:
s1, providing a core body or an initial quantum dot, wherein the initial quantum dot comprises the core body and a first shell layer coated on the outer surface of the core body;
s2, mixing an indium precursor with the core body or the initial quantum dot, and adding a selenium precursor or a selenium precursor and a sulfur precursor at 140-320 ℃ to form a light absorption shell layer on the core body or the initial quantum dot, wherein the light absorption shell layer is a compound containing indium element and selenium element.
8. The method for preparing the core-shell quantum dot according to claim 7, further comprising, after the step S2:
s3, adding a second shell layer precursor at 240-340 ℃ to form a second shell layer on the light absorption shell layer.
9. The method for preparing the core-shell quantum dot according to claim 7, wherein the indium precursor comprises organic indium.
10. A display device comprising the core-shell structure quantum dot according to any one of claims 1 to 6, or the core-shell structure quantum dot prepared by the method according to any one of claims 7 to 9.
CN202011466975.5A 2020-12-14 2020-12-14 Core-shell structure quantum dot, preparation method thereof and display device comprising core-shell structure quantum dot Pending CN113956882A (en)

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CN109401754A (en) * 2018-12-04 2019-03-01 嘉兴纳鼎光电科技有限公司 A kind of quantum dot and preparation method thereof with high blue light absorption rate
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CN109401754A (en) * 2018-12-04 2019-03-01 嘉兴纳鼎光电科技有限公司 A kind of quantum dot and preparation method thereof with high blue light absorption rate
CN110903823A (en) * 2019-12-19 2020-03-24 宁波纳鼎新材料科技有限公司 Selenium-containing quantum dot and synthesis method thereof

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