WO2020108087A1 - 一种量子点发光二极管及其制备方法 - Google Patents

一种量子点发光二极管及其制备方法 Download PDF

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WO2020108087A1
WO2020108087A1 PCT/CN2019/109366 CN2019109366W WO2020108087A1 WO 2020108087 A1 WO2020108087 A1 WO 2020108087A1 CN 2019109366 W CN2019109366 W CN 2019109366W WO 2020108087 A1 WO2020108087 A1 WO 2020108087A1
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quantum dot
dot light
pamam dendrimer
emitting diode
light emitting
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PCT/CN2019/109366
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English (en)
French (fr)
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程陆玲
杨一行
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

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  • the present disclosure relates to the field of quantum dot light-emitting diodes, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • quantum dot light-emitting diodes when quantum dots with exciton Bohr radius much larger than the particle size are used as the material of the light-emitting layer, the resulting device has low luminous efficiency, mainly because the quantum dots and quantum dots in the light-emitting layer There will be exciton energy transfer between them, resulting in a lower quantum yield (QY).
  • QY quantum yield
  • quantum dot light-emitting diodes that use quantum dots with exciton Bohr radius much larger than the particle size as the material of the quantum dot light-emitting layer
  • how to improve the quantum yield of the quantum dot light-emitting layer is the key to improving the luminous efficiency of the quantum dot light-emitting diode.
  • the existing technology is to grow a wide band gap shell layer on the outer layer of quantum dots whose Bohr radius of the excitons is much larger than the particle size, which can reduce the energy transfer between quantum dots and quantum dots to a certain extent, but The quantum yield of this type of quantum dot solid film cannot be greatly improved, so the existing technology needs to be improved.
  • the purpose of the present disclosure is to provide a quantum dot light emitting diode and a preparation method thereof, aiming to solve the low quantum yield of the existing quantum dot material, which leads to the low light emitting efficiency of the quantum dot light emitting diode problem.
  • a quantum dot light-emitting diode includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode, wherein the material of the quantum dot light-emitting layer is a mixture of quantum dots and oil-soluble PAMAM dendrimers Material, the excitonic Bohr radius of the quantum dot is larger than the diameter of the quantum dot.
  • a preparation method of quantum dot light-emitting diode which includes the steps of:
  • the material of the quantum dot light-emitting layer is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers, and the excitonic Bohr radius of the quantum dot is larger than the diameter of the quantum dot.
  • the present disclosure uses a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers to prepare a quantum dot light-emitting layer, and the spatial distance between the quantum dots and the quantum dots in the quantum dot light-emitting layer will be affected by the oil-soluble PAMAM tree
  • the shaped molecules are effectively pulled apart, thereby effectively reducing the energy transfer between quantum dots and quantum dots, and indirectly increasing the fluorescence intensity of the quantum dot light-emitting layer; in addition, when the mixed material forms the quantum dot light-emitting layer, the The oil-soluble PAMAM dendrimers can be wrapped on the surface of quantum dots to further bind the excitons, thereby improving the quantum yield of the quantum dot light-emitting layer and thus improving the luminous efficiency of the quantum dot light-emitting diode.
  • FIG. 1 is a schematic structural diagram of a preferred embodiment of a quantum dot light emitting diode of the present disclosure.
  • FIG. 2 is a flowchart of a method for manufacturing a positive-type quantum dot light-emitting diode of the present disclosure.
  • FIG. 3 is a flow chart of a method for manufacturing an inverse structure quantum dot light emitting diode of the present disclosure.
  • the present disclosure provides a quantum dot light emitting diode and a manufacturing method thereof.
  • a quantum dot light emitting diode and a manufacturing method thereof.
  • the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • quantum dot light-emitting diodes There are many forms of quantum dot light-emitting diodes, and the quantum dot light-emitting diodes are divided into a positive-type structure and an inverse-type structure. Transport layer, quantum dot light emitting layer, hole transport layer, and anode.
  • the positive-type quantum dot light-emitting diode shown in FIG. 1 will be mainly used as an example for introduction. Specifically, as shown in FIG.
  • the positive-type quantum dot light-emitting diode includes a substrate 10, an anode 20, a hole transport layer 30, a quantum dot light-emitting layer 40, and an electron transport layer 50 stacked from bottom to top Cathode 60, wherein the material of the quantum dot light emitting layer is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers, and the excitonic Bohr radius of the quantum dot is larger than the diameter of the quantum dot.
  • the quantum yield of the quantum dot light emitting layer can be effectively improved, thereby improving the luminous efficiency of the quantum dot light emitting diode.
  • the space volume of the oil-soluble PAMAM (polyamide-amine) dendrimer is larger than the diameter of the quantum dot
  • the oil-soluble PAMAM dendrimers can be wrapped on the surface of quantum dots, similar to a molecular shell wrapped on the surface of quantum dots, the oil-soluble PAMAM tree Shaped molecules can further bind the excitons, thereby improving the quantum yield of the solid film, and thereby improving the luminous efficiency of the quantum dot light-emitting diode.
  • the specific preparation method of the oil-soluble PAMAM dendrimer includes the steps of: providing a PAMAM dendrimer; dissolving the PAMAM dendrimer in a polar solvent to prepare a PAMAM dendrimer solution ; Add an end group modifier to the PAMAM dendrimer solution under an inert atmosphere, and mix to make the amine functional group on the PAMAM dendrimer react with the end group modifier to form an oil-soluble group to obtain the oil Soluble PAMAM dendrimer.
  • PAMAM dendrimers without end-group modification are hydrophilic organic molecules, which can be stably stored and dissolved in polar solvents to form a PAMAM dendrimer solution; added to the PAMAM dendrimer solution under an inert atmosphere Excessive end group modifiers and rapid stirring, and by controlling the reaction conditions, can make part or all of the terminal amine functional groups on the PAMAM dendrimer react with the end group modifier, thereby preparing oil-soluble PAMAM dendrimers.
  • the oil-soluble PAMAM dendrimer is a PAMAM dendrimer with a terminal functional group including a sulfonamide group, and the sulfonamide group is -NH-R, where R is unsubstituted aryl, alkyl substitution One or more of aryl and alkylamine substituted aryl.
  • the end group modifier is one selected from p-toluenesulfonyl chloride, o-toluenesulfonyl chloride, m-toluenesulfonyl chloride, p-dimethylaminobenzenesulfonyl chloride, o-dimethylbenzenesulfonyl chloride and m-dimethylaminobenzenesulfonyl chloride Or more, but not limited to this.
  • the reaction formula is:
  • the Dendrimer-NH 2 is a PAMAM dendrimer of the G1-G10 generation, and the PAMAM dendrimer After being modified with end groups, it can be effectively dispersed in the oil phase solution, which is convenient for mixing with the oil phase quantum dots to form a solid film.
  • the oil-soluble PAMAM dendrimer is selected from the first generation PAMAM dendrimer (G1), the second generation PAMAM dendrimer (G2), the third generation PAMAM dendrimer (G3), the first Fourth generation PAMAM dendrimer (G4), fifth generation PAMAM dendrimer (G5), sixth generation PAMAM dendrimer (G6), seventh generation PAMAM dendrimer (G7), eighth generation PAMAM dendrimer (G8), one or more of the ninth generation PAMAM dendrimer (G9) and the tenth generation PAMAM dendrimer (G10), etc., but not limited thereto.
  • the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular units A (ethylenediamine) and molecular units B (methyl acrylate), and the PAMAM dendrimer can be obtained by a divergent method Synthesis, the first step is the reaction of ethylenediamine and methyl acrylate to produce carboxylic acid ester. The second step is to react the obtained carboxylic acid ester with excess ethylenediamine. After the above two steps, the first generation of PAMAM can be prepared For dendrimers, repeat the above two steps to obtain higher algebraic PAMAM dendrimers.
  • the general formulas of molecular unit A and molecular unit B contained in PAMAM dendrimers of different algebras are: A(2 n +2 n-1 +...+2 n-3 )+B(2 n+1 +2 n + ....+2 n-1 ), where the value of n is 3-10; in addition, the general formula of the first generation PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B, the second generation PAMAM dendrimer The general formula of the molecule containing molecular unit A and molecular unit B is 5A+8B.
  • the algebra of the PAMAM dendrimer becomes larger, its spatial volume also becomes larger.
  • the PAMAM dendrimer with a larger algebra is selected to match the quantum dot to form a mixed material; when the Bohr radius of the selected quantum dots is relatively small, the algebra is selected to be smaller
  • the PAMAM dendrimer is matched with the quantum dots to form a mixed material.
  • the difference between the Bohr radius of the quantum dot and the diameter of the quantum dot is controlled to 6-100 nm
  • the oil-soluble PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer and the sixth generation PAMAM tree
  • the seventh generation PAMAM dendrimer, the eighth generation PAMAM dendrimer, the ninth generation PAMAM dendrimer, and the tenth generation PAMAM dendrimer is controlled to 6-100 nm
  • the oil-soluble PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer and the sixth generation PAMAM tree
  • the seventh generation PAMAM dendrimer, the eighth generation PAMAM dendrimer, the ninth generation PAMAM dendrimer, and the tenth generation PAMAM dendrimer are examples of the shape molecule, the seventh generation PAMAM dendrimer, the eighth generation PAMAM dendrimer, the ninth generation PAMAM dendrimer, and the tenth generation PAMAM dendrim
  • the mixing of the PAMAM dendrimers and quantum dots can not only increase the distance between quantum dots , Can also improve the film-forming properties of quantum dots.
  • the difference between the Bohr radius of the quantum dot and the diameter of the quantum dot is controlled to be 20-40 nm, and the oil-soluble PAMAM dendrimer is selected from the sixth generation PAMAM One or two of the dendrimer and the seventh generation PAMAM dendrimer.
  • the oil-soluble PAMAM dendrimers and quantum dots should be Mixed in a certain ratio to form a mixed material. Because PAMAM dendrimers of different generations have large molecular weight differences, when using different generations of PAMAM dendrimers and quantum dots to form a mixed material, their molar mass ratios are quite different.
  • the PAMAM dendrimer is a fifth-generation PAMAM dendrimer
  • the ratio of the molar amount of the fifth-generation PAMAM dendrimer to the mass of quantum dots is 1-5 mmol: 10 mg.
  • the ratio of the molar amount of the sixth-generation PAMAM dendrimer to the mass of quantum dots is 0.5-4 mmol: 10 mg.
  • the PAMAM dendrimer is a seventh-generation PAMAM dendrimer
  • the molar ratio of the seventh-generation PAMAM dendrimer to the mass of quantum dots is 0.3-3 mmol: 10 mg.
  • the ratio of the molar amount of the eighth generation PAMAM dendrimer to the mass of quantum dots is 0.2-2 mmol: 10 mg.
  • the PAMAM dendrimer is a ninth-generation PAMAM dendrimer
  • the molar ratio of the ninth-generation PAMAM dendrimer to the mass of quantum dots is 0.1-1 mmol: 10 mg.
  • the ratio of the molar amount of the tenth generation PAMAM dendrimer to the mass of quantum dots is 0.05-0.5 mmol: 10 mg.
  • the quantum dots are oil phase quantum dots, and the oil phase quantum dots are selected from one or more of PbS, PbSe, CdTe, HgS, AgS, and InP, but are not limited thereto.
  • the present disclosure also provides a quantum dot light-emitting diode with an inverted structure, which includes a substrate stacked in this order from bottom to top, a cathode, an electron transport layer, a quantum dot light-emitting layer, a hole transport layer, and an anode ,
  • the material of the quantum dot light-emitting layer is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers, and the excitonic Bohr radius of the quantum dot is larger than the diameter of the quantum dot.
  • the present disclosure is not limited to the quantum dot light-emitting diode of the above structure, and may further include an interface function layer or an interface modification layer, including but not limited to an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer One or more.
  • the quantum dot light emitting diode of the present disclosure may be partially encapsulated, fully encapsulated, or unencapsulated.
  • the material of the anode is selected from doped metal oxides; wherein, the doped metal oxides include but are not limited to indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), Antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), aluminum-doped magnesium oxide One or more of (AMO).
  • ITO indium-doped tin oxide
  • FTO fluorine-doped tin oxide
  • ATO Antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • IZO indium-doped zinc oxide
  • MZO magnesium-doped zinc oxide
  • AMO aluminum-doped magnesium oxide
  • AMO aluminum-doped magnesium oxide
  • the material of the hole transport layer is selected from organic materials with good hole transport capabilities, such as but not limited to poly(9,9-dioctylfluorene-CO-N-(4- (Butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) ( Poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4”-tri(carb Azole-9-yl) triphenylamine (TCTA), 4,4'-bis(9-carbazole) biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methyl Phenyl)-1,1'-biphenyl-4,4'
  • the electron transport layer material includes, but is not limited to, one or more of zinc oxide, nickel oxide, and titanium oxide.
  • the material of the cathode is selected from one or more of conductive carbon materials, conductive metal oxide materials and metal materials; wherein the conductive carbon materials include but are not limited to doped or undoped carbon nanotubes , One or more of doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber and porous carbon; conductive metal oxide materials include but are not limited to ITO, FTO, ATO And one or more of AZO; metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or their alloys; wherein, among the metal materials, their morphologies include but are not limited to dense thin films, nanowires, One or more of nanospheres, nanorods, nanocones and hollow nanospheres.
  • quantum dot light-emitting diodes are divided into a positive structure and an inverse structure.
  • the positive structure includes an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode.
  • the anode of the positive structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light emitting layer.
  • Hole functional layer such as a layer, a hole injection layer and an electron blocking layer, and an electron functional layer such as an electron transport layer, an electron injection layer and a hole blocking layer may also be provided between the cathode and the quantum dot light emitting layer.
  • the inversion structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
  • the cathode of the inversion structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light-emitting layer.
  • the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
  • the bottom electrode provided on the substrate is an anode.
  • the substrate may be provided with a bottom electrode on the substrate; in yet another embodiment of the present disclosure
  • the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a hole transport layer stacked on the surface of the substrate; in yet another embodiment of the present disclosure, the substrate may include a substrate, A bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the substrate, and a hole transport layer stacked on the surface of the hole injection layer; in still another embodiment of the present disclosure, the substrate It may include a substrate, a bottom electrode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the substrate, a hole transport layer stacked on the surface of the hole injection layer, and a layer stacked on the surface of the hole transport layer Electron blocking layer.
  • the bottom electrode provided on the substrate is a cathode.
  • the substrate may be provided with a bottom electrode on the substrate; in yet another embodiment of the present disclosure
  • the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate and an electron transport layer stacked on the surface of the substrate; in yet another embodiment of the present disclosure, the substrate may include a substrate and a stack A bottom electrode provided on the surface of the substrate, an electron injection layer stacked on the surface of the substrate, and a hole transport layer stacked on the surface of the electron injection layer; in still another embodiment of the present disclosure, the substrate may include a substrate The bottom, the bottom electrode stacked on the surface of the substrate, the electron injection layer stacked on the surface of the substrate, the electron transport layer stacked on the surface of the electron injection layer, and the hole blocking layer stacked on the surface of the electron transport layer.
  • the present disclosure also provides an embodiment of a method for manufacturing a quantum dot light-emitting diode with a positive structure as shown in FIG. 1, as shown in FIG. 2, including the following steps:
  • a quantum dot light-emitting layer is prepared on the hole transport layer, wherein the quantum dot light-emitting layer material is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers, and the excitons of the quantum dots The radius is larger than the diameter of the quantum dot;
  • each layer preparation method may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, and co-precipitation method One or more; physical methods include but are not limited to solution methods (such as spin coating method, printing method, knife coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating method) Or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion plating method, etc.), deposition method (such as physical vapor deposition method, atomic layer One or more of deposition method, pulsed laser deposition method, etc.).
  • solution methods such as spin coating method, printing method, knife coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating
  • the step of preparing a quantum dot light emitting layer on the hole transport layer includes:
  • the present disclosure uses a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers to prepare a quantum dot light-emitting layer, and the spatial distance between quantum dots and quantum dots in the quantum dot light-emitting layer will be effectively affected by oil-soluble PAMAM dendrimers To effectively reduce the energy transfer between quantum dots and quantum dots, and indirectly increase the fluorescence intensity of the quantum dot light-emitting layer; in addition, when the mixed material forms the quantum dot light-emitting layer, the oil-soluble PAMAM The dendritic molecules can be wrapped on the surface of the quantum dots, further binding the excitons, thereby improving the quantum yield of the quantum dot light emitting layer, and thereby improving the luminous efficiency of the quantum dot light emitting diode.
  • the present disclosure also provides a method for preparing a QLED containing a hole-transporting layer of an inverse structure, as shown in FIG. 3, including the following steps:
  • a quantum dot light-emitting layer is prepared on the electron transport layer.
  • the material of the quantum dot light-emitting layer is a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers.
  • the excitons Bohr radius of the quantum dots is larger than that of quantum dots. diameter;
  • the preparation method of the above layers may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-precipitation method or A variety of; physical methods include but are not limited to physical coating method or solution method, wherein the solution method includes but not limited to spin coating method, printing method, blade coating method, dipping method, dipping method, spraying method, roll coating method, casting Method, slot coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, One or more of atomic layer deposition and pulsed laser deposition.
  • the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-pre
  • the present disclosure uses a mixed material composed of quantum dots and oil-soluble PAMAM dendrimers to prepare a quantum dot light-emitting layer, and the spatial distance between quantum dots and quantum dots in the quantum dot light-emitting layer will be oil-soluble PAMAM dendrimers are effectively pulled apart, thereby effectively reducing the energy transfer between quantum dots and quantum dots, indirectly increasing the fluorescence intensity of the quantum dot light-emitting layer; in addition, when the mixed material forms the quantum dot light-emitting layer, The oil-soluble PAMAM dendrimers can be wrapped on the surface of quantum dots to further bind the excitons, thereby improving the quantum yield of the quantum dot light-emitting layer, thereby improving the luminous efficiency of the quantum dot light-emitting diode.

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Abstract

一种量子点发光二极管及其制备方法，该量子点发光二极管包括阴极（60）、阳极（20）以及设置在该阴极（60）和阳极（20）之间的量子点发光层（40），该量子点发光层（40）材料为由量子点和油溶性PAMAM树形分子组成的混合材料，该量子点的激子波尔半径大于量子点的直径。其中，该量子点发光层（40）中的量子点之间的空间距离会被油溶性PAMAM树形分子有效的拉开，从而有效地降低了量子点之间的能量转移，间接地提高了量子点发光层的荧光强度；另外，该油溶性PAMAM树形分子可包裹在量子点表面，对激子进行束缚，从而可提高量子点发光层的量子产率，进而提高量子点发光二极管的发光效率。

Description

一种量子点发光二极管及其制备方法 技术领域
本公开涉及量子点发光二极管领域，尤其涉及一种量子点发光二极管及其制备方法。
背景技术
在量子点发光二极管中，利用激子波尔半径远大于颗粒粒径的量子点作为发光层材料时，制得的器件发光效率较低，其主要原因是因为发光层中的量子点与量子点之间会产生激子能量转移，从而造成量子产率(QY)较低。
对于以激子波尔半径远大于颗粒粒径的量子点作为量子点发光层材料的量子点发光二极管而言，如何提高量子点发光层的量子产率是提升量子点发光二极管发光效率的关键。现有的技术是对该类激子波尔半径远大于颗粒粒径的量子点在外层生长一层宽带隙壳层，这能够在一定程度上降低量子点与量子点之间的能量转移，但不能够大幅的改善该类量子点固态膜的量子产率，因此现有技术有待改进。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点发光二极管及其制备方法，旨在解决现有量子点材料的量子产率较低，导致量子点发光二极管发光效率较低的问题。
本公开的技术方案如下：
一种量子点发光二极管，包括阴极、阳极以及设置在所述阴极和阳极之间的量子点发光层，其中，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径。
一种量子点发光二极管的制备方法，其中，包括步骤：
提供一基板，在所述基板表面制备量子点发光层；
其中，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材 料，所述量子点的激子波尔半径大于量子点的直径。
有益效果：本公开采用由量子点和油溶性PAMAM树形分子组成的混合材料制备量子点发光层，所述量子点发光层中的量子点与量子点之间的空间距离会被油溶性PAMAM树形分子有效的拉开，从而有效地降低量子点与量子点之间的能量转移，间接地提高了量子点发光层的荧光强度；另外，当所述混合材料形成量子点发光层后，所述油溶性PAMAM树形分子可包裹在量子点表面，进一步地对激子进行束缚，从而提高量子点发光层的量子产率，进而提高量子点发光二极管的发光效率。
附图说明
图1为本公开一种量子点发光二极管较佳实施例的结构示意图。
图2为本公开一种正型结构的量子点发光二极管的制备方法流程图。
图3为本公开一种反型结构的量子点发光二极管的制备方法流程图。
具体实施方式
本公开提供一种量子点发光二极管及其制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
量子点发光二极管有多种形式，且所述量子点发光二极管分为正型结构和反型结构，所述反型结构的量子点发光二极管可包括从下往上层叠设置的基板、阴极、电子传输层、量子点发光层、空穴传输层以及阳极。而本公开的具体实施方式中将主要以如图1所示的正型结构的量子点发光二极管为实施例进行介绍。具体地，如图1所示，所述正型结构的量子点发光二极管包括从下往上层叠设置的基板10、阳极20、空穴传输层30、量子点发光层40、电子传输层50以及阴极60，其中，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径。
本实施例通过采用由量子点和油溶性PAMAM树形分子组成的混合材料作为量子 点发光层材料，能够有效提升量子点发光层的量子产率，从而提升量子点发光二极管的发光效率。实现上述效果的机理具体如下：
所述混合材料中，由于油溶性PAMAM(聚酰胺-胺)树形分子的空间体积比量子点的直径要大，当采用所述混合材料制备成固态膜(量子点发光层)后，所述固态膜中的量子点与量子点之间的空间距离会被油溶性PAMAM树形分子有效的拉开，从而有效地降低了量子点与量子点之间的能量转移，间接地提高了固态膜的荧光强度；另外，当所述混合材料形成固态膜后，所述油溶性PAMAM树形分子可包裹在量子点表面，类似于在量子点表面包裹了一层分子壳层，所述油溶性PAMAM树形分子可进一步地对激子进行束缚，从而提高固态膜的量子产率，进而提高量子点发光二极管的发光效率。
在本实施例中，所述油溶性PAMAM树形分子的具体制备方法包括步骤：提供一种PAMAM树形分子；将所述PAMAM树形分子溶解在极性溶剂中，制得PAMAM树形分子溶液；在惰性气氛下向所述PAMAM树形分子溶液中加入端基修饰剂，混合使所述PAMAM树形分子上的胺基官能团与端基修饰剂发生反应生成油溶性基团，得到所述油溶性PAMAM树形分子。
未经过端基修饰的PAMAM树形分子为亲水性有机分子，其可以稳定存放并溶解在极性溶剂中，形成PAMAM树形分子溶液；在惰性气氛下向所述PAMAM树形分子溶液中加入过量的端基修饰剂并快速搅拌，并通过控制反应条件，可使PAMAM树形分子上末梢的胺基官能团部分或全部与端基修饰剂发生反应，从而制得油溶性PAMAM树形分子。在一些实施方式中，所述油溶性PAMAM树形分子为末梢官能团包括磺酰胺基的PAMAM树形分子，所述磺酰胺基为-NH-R，其中R为未取代的芳基、烷基取代的芳基和烷胺基取代的芳基中的一种或多种。所述端基修饰剂选自对甲苯磺酰氯、邻甲苯磺酰氯、间甲苯磺酰氯、对二甲氨基苯磺酰氯、邻二甲基苯磺酰氯和间二甲氨基苯磺酰氯中的一种或多种，但不限于此。作为举例，当向PAMAM树形分子溶液中加入对二甲氨基苯磺酰氯时，其反应式为：
Dendrimer-NH 2+(CH 3) 2-N-C 10H 6-SOCl→Dendrimer-NHOS-C 10H 6-N-(CH 3) 2+HCl；
当向PAMAM树形分子溶液中加入对甲苯磺酰氯时，其反应式为：
Dendrimer-NH 2+CH 3-C 6H 4-SOOCl→Dendrimer-NHSOO-C 6H 4-CH 3；所述Dendrimer-NH 2为G1-G10代的PAMAM树形分子，所述PAMAM树形分子在经过端基修饰后能够有效分散在油相溶液中，便于与油相量子点混合形成固态膜。
在一些实施方式中，所述油溶性PAMAM树形分子选自第一代PAMAM树形分子(G1)、第二代PAMAM树形分子(G2)、第三代PAMAM树形分子(G3)、第四代PAMAM树形分子(G4)、第五代PAMAM树形分子(G5)、第六代PAMAM树形分子(G6)、第七代PAMAM树形分子(G7)、第八代PAMAM树形分子(G8)、第九代PAMAM树形分子(G9)和第十代PAMAM树形分子(G10)等中的一种或多种，但不限于此。
本实施例中，所述PAMAM(聚酰胺-胺)树形分子是由不同的分子单元A(乙二胺)和分子单元B(丙烯酸甲酯)反应得到，所述PAMAM树形分子可由发散法合成，第一步由乙二胺和丙烯酸甲酯反应生成羧酸酯，第二步将得到的羧酸酯与过量的乙二胺反应，经过上述两步反应后即可制得第一代PAMAM树形分子，重复上述两步反应即可得到更高代数的PAMAM树形分子。不同代数的PAMAM树形分子所含有的分子单元A和分子单元B的通式为：A(2 n+2 n-1+…+2 n-3)+B(2 n+1+2 n+….+2 n-1)，其中n的取值为3-10；另外，第一代PAMAM树形分子含有分子单元A和分子单元B的通式为A+4B，第二代PAMAM树形分子含有分子单元A和分子单元B的通式为5A+8B。
在一些实施方式中，由于随着PAMAM树形分子的代数变大，其空间体积也越大，为保证PAMAM树形分子能够有效地将量子点与量子点之间的空间距离拉大，当选用的量子点的波尔半径相对较大时，则选择代数较大的PAMAM树形分子与所述量子点匹配形成混合材料；当选用的量子点的波尔半径相对较小时，则选择代数较小的PAMAM树形分子与所述量子点匹配形成混合材料。在一些实施方式中，将量子点的波尔半径与量子点的直径之间相差控制为6-100nm，所述油溶性PAMAM树形分子选自第五代PAMAM树形分子、第六代PAMAM树形分子、第七代PAMAM树形分子、第八代PAMAM树形分子、第九代PAMAM树形分子和第十代PAMAM树形分子中的一种或多种。由于PAMAM树形分子随着代数的增加不仅其空间体积变大，而且其粘度系数也随着增大，因此，所述PAMAM树形分子与量子点混合后不仅能够增大量子点之间的距 离，还能够改善量子点的成膜性能。在一些实施方式中，为保证发光层整体的亮度，将量子点的波尔半径与量子点的直径之间相差控制为为20-40nm，所述油溶性PAMAM树形分子选自第六代PAMAM树形分子和第七代PAMAM树形分子中一种或两种。
在一些实施方式中，为保证量子点之间的空间距离能被PAMAM树形分子拉开，从而减小量子点之间的能量转移，应将所述油溶性PAMAM树形分子与量子点按照设定的比例进行混合形成混合材料。由于不同代数的PAMAM树形分子，其分子量差异较大，因此，当选用不同代数的PAMAM树形分子与量子点组成混合材料时，其摩尔质量比差异较大。
在一些实施方式中，若所述PAMAM树形分子为第五代PAMAM树形分子，则所述第五代PAMAM树形分子的摩尔量与量子点的质量之比为1-5mmol:10mg。
在一些实施方式中，若所述PAMAM树形分子为第六代PAMAM树形分子，则所述第六代PAMAM树形分子的摩尔量与量子点的质量之比为0.5-4mmol:10mg。
在一些实施方式中，若所述PAMAM树形分子为第七代PAMAM树形分子，则所述第七代PAMAM树形分子的摩尔量与量子点的质量之比为0.3-3mmol:10mg。
在一些实施方式中，若所述PAMAM树形分子为第八代PAMAM树形分子，则所述第八代PAMAM树形分子的摩尔量与量子点的质量之比为0.2-2mmol:10mg。
在一些实施方式中，若所述PAMAM树形分子为第九代PAMAM树形分子，则所述第九代PAMAM树形分子的摩尔量与量子点的质量之比为0.1-1mmol:10mg。
在一些实施方式中，若所述PAMAM树形分子为第十代PAMAM树形分子，则所述第十代PAMAM树形分子的摩尔量与量子点的质量之比为0.05-0.5mmol:10mg。
在一些实施方式中，所述量子点为油相量子点，所述油相量子点选自PbS、PbSe、CdTe、HgS、AgS和InP中的一种或多种，但不限于此。
在一些实施方式中，本公开还提供一种反型结构的量子点发光二极管，其包括从下往上依次层叠设置的基板，阴极、电子传输层、量子点发光层、空穴传输层和阳极，其中，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径。
需说明的是，本公开不限于上述结构的量子点发光二极管，还可进一步包括界面功能层或界面修饰层，包括但不限于电子阻挡层、空穴阻挡层、电极修饰层、隔离保护层中的一种或多种。本公开所述量子点发光二极管可以部分封装、全封装或不封装。
在一些实施方式中，所述阳极的材料选自掺杂金属氧化物；其中，所述掺杂金属氧化物包括但不限于铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)、铝掺杂氧化锌(AZO)、镓掺杂氧化锌(GZO)、铟掺杂氧化锌(IZO)、镁掺杂氧化锌(MZO)、铝掺杂氧化镁(AMO)中的一种或多种。
在一些实施方式中，所述空穴传输层的材料选自具有良好空穴传输能力的有机材料，例如可以为但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4’,4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)、掺杂石墨烯、非掺杂石墨烯和C60中的一种或多种。
在一些实施方式中，所述电子传输层材料包括但不限于氧化锌、氧化镍和氧化钛中的一种或多种。
在一些实施方式中，所述阴极的材料选自导电碳材料、导电金属氧化物材料和金属材料中的一种或多种；其中导电碳材料包括但不限于掺杂或非掺杂碳纳米管、掺杂或非掺杂石墨烯、掺杂或非掺杂氧化石墨烯、C60、石墨、碳纤维和多孔碳中的一种或多种；导电金属氧化物材料包括但不限于ITO、FTO、ATO和AZO中的一种或多种；金属材料包括但不限于Al、Ag、Cu、Mo、Au、或它们的合金；其中所述金属材料中，其形态包括但不限于致密薄膜、纳米线、纳米球、纳米棒、纳米锥和纳米空心球中的一种或多种。
具体的，量子点发光二极管分正型结构和反型结构。正型结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，正型结构的阳极设置在衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层， 在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。反型结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层，反型结构的阴极设置在衬底上，在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层，在阴极和量子点发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层。
对于正型器件而言，设置在衬底上的底电极为阳极，在本公开的一种实施方式中，所述基板可以为衬底上设置底电极；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极和层叠设置在衬底表面的空穴传输层；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的空穴注入层和层叠设置在空穴注入层表面的空穴传输层；在本公开的还一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的空穴注入层、层叠设置在空穴注入层表面的空穴传输层和层叠设置在空穴传输层表面的电子阻挡层。
对于反型器件而言，设置在衬底上的底电极为阴极，在本公开的一种实施方式中，所述基板可以为衬底上设置底电极；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极和层叠设置在衬底表面的电子传输层；在本公开的又一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的电子注入层和层叠设置在电子注入层表面的空穴传输层；在本公开的还一种实施方式中，所述基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在衬底表面的电子注入层、层叠设置在电子注入层表面的电子传输层和层叠设置在电子传输层表面的空穴阻挡层。
进一步地，本公开还提供一种如图1所示正型结构的量子点发光二极管的制备方法的实施例，如图2所示，包括以下步骤：
S10、提供一衬底，在所述衬底上制备阳极；
S20、在所述阳极上制备空穴传输层；
S30、在所述空穴传输层上制备量子点发光层，其中，所述量子点发光层材料为由 量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径；
S40、在所述量子点发光层上制备电子传输层；
S50、在所述电子传输层上制备阴极，得到所述量子点发光二极管。
本公开中，各层制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于溶液法(如旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法或条状涂布法等)、蒸镀法(如热蒸镀法、电子束蒸镀法、磁控溅射法或多弧离子镀膜法等)、沉积法(如物理气相沉积法、原子层沉积法、脉冲激光沉积法等)中的一种或多种。
在一些实施方式中，在所述空穴传输层上制备量子点发光层的步骤包括：
将所述混合材料溶解在非极性溶剂中，生成胶体溶液；
在所述空穴传输层表面沉积所述胶体溶液成膜，在80-150℃条件下退火处理15-60min，制得量子点发光层。
本公开采用由量子点和油溶性PAMAM树形分子组成的混合材料制备量子点发光层，所述量子点发光层中的量子点与量子点之间的空间距离会被油溶性PAMAM树形分子有效的拉开，从而有效地降低量子点与量子点之间的能量转移，间接地提高了量子点发光层的荧光强度；另外，当所述混合材料形成量子点发光层后，所述油溶性PAMAM树形分子可包裹在量子点表面，进一步地对激子进行束缚，从而提高量子点发光层的量子产率，进而提高量子点发光二极管的发光效率。
本公开还提供一种反型结构的含空穴传输层的QLED的制备方法，如图3所示，包括如下步骤：
S100、提供一衬底，在所述衬底上制备阴极；
S200、在所述阴极上制备电子传输层；
S300、在电子传输层上制备量子点发光层，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径；
S400、在量子点发光层上制备空穴传输层；
S500、在空穴传输层上制备阳极，得到QLED。
上述各层的制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于物理镀膜法或溶液法，其中溶液法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
综上所述，本公开采用由量子点和油溶性PAMAM树形分子组成的混合材料制备量子点发光层，所述量子点发光层中的量子点与量子点之间的空间距离会被油溶性PAMAM树形分子有效的拉开，从而有效地降低量子点与量子点之间的能量转移，间接地提高了量子点发光层的荧光强度；另外，当所述混合材料形成量子点发光层后，所述油溶性PAMAM树形分子可包裹在量子点表面，进一步地对激子进行束缚，从而提高量子点发光层的量子产率，进而提高量子点发光二极管的发光效率。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (20)

  1. 一种量子点发光二极管，包括阴极、阳极以及设置在所述阴极和阳极之间的量子点发光层，其特征在于，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径。
  2. 根据权利要求1所述量子点发光二极管，其特征在于，所述油溶性PAMAM树形分子为末梢官能团包括磺酰胺基的PAMAM树形分子，所述磺酰胺基为-NH-R，其中R为未取代的芳基、烷基取代的芳基和烷胺基取代的芳基中的一种或多种。
  3. 根据权利要求2所述的量子点发光二极管，其特征在于，所述PAMAM树形分子选自第五代至第十代PAMAM树形分子中的一种或多种。
  4. 根据权利要求3所述的量子点发光二极管，其特征在于，所述PAMAM树形分子选自第六代或第七代PAMAM树形分子中的一种或多种。
  5. 根据权利要求2所述的量子点发光二极管，其特征在于，所述混合材料中，若所述PAMAM树形分子为第五代PAMAM树形分子，则所述第五代PAMAM树形分子的摩尔量与量子点的质量之比为1-5mmol:10mg。
  6. 根据权利要求2所述的量子点发光二极管，其特征在于，若所述PAMAM树形分子为第六代PAMAM树形分子，则所述第六代PAMAM树形分子的摩尔量与量子点的质量之比为0.5-4mmol:10mg。
  7. 根据权利要求2所述的量子点发光二极管，其特征在于，若所述PAMAM树形分子为第七代PAMAM树形分子，则所述第七代PAMAM树形分子的摩尔量与量子点的质量之比为0.3-3mmol:10mg。
  8. 根据权利要求2所述的量子点发光二极管，其特征在于，若所述PAMAM树形分子为第八代PAMAM树形分子，则所述第八代PAMAM树形分子的摩尔量与量子点的质量之比为0.2-2mmol:10mg。
  9. 根据权利要求2所述的量子点发光二极管，其特征在于，若所述PAMAM树形分子为第九代PAMAM树形分子，则所述第九代PAMAM树形分子的摩尔量与量子点的质量之比为0.1-1mmol:10mg。
  10. 根据权利要求2所述的量子点发光二极管，其特征在于，若所述PAMAM树形 分子为第十代PAMAM树形分子，则所述第十代PAMAM树形分子的摩尔量与量子点的质量之比为0.05-0.5mmol:10mg。
  11. 根据权利要求1所述的量子点发光二极管，其特征在于，所述阳极和所述量子点发光层之间还设置有空穴传输层。
  12. 根据权利要求11所述的量子点发光二极管，其特征在于，所述空穴传输层材料选自TFB、PVK、Poly-TPD、PFB、TCTA、CBP、TPD、NPB、掺杂石墨烯、非掺杂石墨烯和C60中的一种或多种。
  13. 根据权利要求1所述的量子点发光二极管，其特征在于，所述阴极和所述量子点发光层之间还设置有电子传输层。
  14. 根据权利要求13所述的量子点发光二极管，其特征在于，所述电子传输层选自氧化锌、氧化镍和氧化钛中的一种或多种。
  15. 根据权利要求1所述的量子点发光二极管，其特征在于，所述量子点选自PbS、PbSe、CdTe、HgS、AgS和InP中的一种或多种。
  16. 一种量子点发光二极管的制备方法，其特征在于，包括步骤：
    提供一种基板，在所述基板表面制备量子点发光层；
    其中，所述量子点发光层材料为由量子点和油溶性PAMAM树形分子组成的混合材料，所述量子点的激子波尔半径大于量子点的直径。
  17. 根据权利要求16所述量子点发光二极管的制备方法，其特征在于，所述油溶性PAMAM树形分子的制备方法包括步骤：
    将PAMAM树形分子溶解在极性溶剂后加入端基修饰剂，混合使所述PAMAM树形分子上末梢的胺基官能团全部或部分与端基修饰剂发生反应，得到所述油溶性PAMAM树形分子。
  18. 根据权利要求17所述量子点发光二极管的制备方法，其特征在于，所述端基修饰剂选自对甲苯磺酰氯、邻甲苯磺酰氯、间甲苯磺酰氯、对二甲氨基苯磺酰氯、邻二甲基苯磺酰氯和间二甲氨基苯磺酰氯中的一种或多种。
  19. 根据权利要求18所述量子点发光二极管的制备方法，在所述基板表面制备量 子点发光层的步骤包括：
    采用溶液法在所述基板沉积所述混合材料后退火，制得所述量子点发光层。
  20. 根据权利要求19所述量子点发光二极管的制备方法，其特征在于，在所述基板表面制备量子点发光层的步骤包括：
    采用溶液法在所述基板沉积所述混合材料，在80-150℃条件下退火处理15-60min，制得所述量子点发光层。
PCT/CN2019/109366 2018-11-28 2019-09-30 一种量子点发光二极管及其制备方法 WO2020108087A1 (zh)

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