WO2020108069A1 - 一种纳米金属氧化物及其制备方法、量子点发光二极管 - Google Patents

一种纳米金属氧化物及其制备方法、量子点发光二极管 Download PDF

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WO2020108069A1
WO2020108069A1 PCT/CN2019/108329 CN2019108329W WO2020108069A1 WO 2020108069 A1 WO2020108069 A1 WO 2020108069A1 CN 2019108329 W CN2019108329 W CN 2019108329W WO 2020108069 A1 WO2020108069 A1 WO 2020108069A1
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metal oxide
nano metal
composite material
pamam dendrimer
quantum dot
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程陆玲
杨一行
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TCL Technology Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

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  • the present disclosure relates to the field of nano metal oxide passivation, in particular to a nano metal oxide and its preparation method and quantum dot light emitting diode.
  • Quantum dot light-emitting diode (QLED) device efficiency, life and other technical indicators are closely related to each functional layer in the device, where the electron transport layer affects the charge injection level of the device.
  • Metal oxide nanoparticles are the main materials used in quantum dot light-emitting diodes.
  • the electron mobility and energy band width of metal oxide nanoparticles are the key technologies that affect the device. Therefore, the preparation of suitable electron mobility and energy band width Metal oxides are more important.
  • the surface of the metal oxide nanoparticles prepared by the conventional synthesis method has many defects, which not only affects the electron mobility but also other functional layers of QLED.
  • the purpose of the present disclosure is to provide a method for preparing a nano metal oxide, which aims to solve the problem that many defects exist on the surface of the existing nano metal oxide.
  • a method for preparing nano metal oxide which comprises the steps of:
  • a composite material including PAMAM dendrimers and metal ions bound in the cavity of the PAMAM dendrimers;
  • the composite material and the initial nano metal oxide are mixed in a polar solvent, and the metal ions in the composite material are ionized and coordinately combined with oxygen vacancies on the surface of the initial nano metal oxide to obtain the nano metal oxide.
  • a nano metal oxide which is prepared by the method of the present disclosure.
  • a quantum dot light emitting diode includes an electron transport layer, wherein the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure or a nano metal oxide described in the present disclosure.
  • the present disclosure provides a method for preparing a nano metal oxide.
  • a PAMAM dendrimer combined with metal ions in the cavity as a passivation precursor, the surface of the initial nano metal oxide is passivated to obtain a surface Nano metal oxide with fewer defects.
  • FIG. 1 is a flowchart of a preferred embodiment of a method for preparing a nano metal oxide according to the present disclosure.
  • the present disclosure provides a nano metal oxide, a preparation method thereof, and a quantum dot light emitting diode.
  • a nano metal oxide a preparation method thereof, and a quantum dot light emitting diode.
  • the present disclosure provides a flow chart of a preferred embodiment of a method for preparing a nano metal oxide. As shown in the figure, the method includes the following steps:
  • a PAMAM dendrimer combined with metal ions in the cavity is used as a passivation precursor, and the surface passivation treatment of the initial nano metal oxide can produce a nano metal oxide with fewer surface defects.
  • the mechanism for achieving the above effects is as follows:
  • the composite material provided by the present disclosure and the nano-metal oxide are mixed in a polar solvent environment, and metal ions in the composite material will be ionized.
  • Nano-metal oxides with oxygen vacancies on the surface are more prone to chemical coordination when they encounter free metal ions, so that the free metal ions are coordinated and incorporated into the oxygen vacancies on the surface of the nano-metal oxide. Therefore, in this embodiment, after the composite material is mixed with the initial nano metal oxide, the metal ions in the PAMAM dendrimer can be coordinated and bound to the oxygen vacancy of the initial nano metal oxide after ionization, thereby reducing the surface of the nano metal oxide defect.
  • the method for preparing the composite material includes the steps of: providing a PAMAM dendrimer; adding the PAMAM dendrimer to a metal ion solution, and mixing the N atoms in the PAMAM dendrimer cavity with The metal ions are coordinated and combined to obtain a composite material.
  • 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 formula of molecular unit A and molecular unit B contained in PAMAM dendrimers of different algebras is: 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;
  • the general formula of the first generation PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B
  • the second The generation PAMAM dendrimer contains molecular unit A and molecular unit B with the general formula 5A+8B.
  • the number of metal ions that can be combined by different generations of PAMAM dendrimers is different.
  • the main reason is that different generations of PAMAM dendrimers can coordinate metal ions.
  • the generation of PAMAM dendrimers is from the first generation to In the fourth generation, due to its low density of terminal functional groups (amine groups), it is not easy to be used as a carrier for adsorbing metal ions.
  • the PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer (G5), the sixth generation PAMAM dendrimer (G6), the seventh generation PAMAM dendrimer (G7), and the eighth generation PAMAM One or more of dendrimer (G8), ninth generation PAMAM dendrimer (G9), tenth generation PAMAM dendrimer (G10), etc.
  • the algebra of the PAMAM dendrimer is G5-G10
  • the functional groups and functional groups can form a complete and The closed cavity, so the PAMAM dendrimers of the G5-G10 generation can be used as candidate materials for the coordination with metal ions.
  • the preparation method described in this example Composite materials can be stably stored in polar solvents.
  • the polar solvent is selected from one of ethanol, water, or methanol.
  • the element type of the metal ion is selected from one or more of Au, Ag, Cu, Fe, Ni, Zn, and Mo, but is not limited thereto.
  • the composite material and the initial nano metal oxide are mixed in a polar solvent according to a predetermined ratio, and the metal ions in the composite material are ionized and coordinately combined with oxygen vacancies on the surface of the initial nano metal oxide, The nano metal oxide is obtained.
  • the metal ions in the composite material in this embodiment can efficiently coordinate with the oxygen vacancy on the surface of the nano metal oxide, and will not introduce other unnecessary anions to affect the passivation effect of the nano metal oxide.
  • the conventional preparation methods of the nano metal oxide include a precipitation method, a sol-gel method, and a microemulsion method, etc., which are mainly prepared by the sol-gel method.
  • the sol-gel method refers to: dissolving a metal salt (such as zinc acetate, etc.) in an organic solvent (such as ethanol), adjusting the pH value by an organic base and preparing the metal salt solution by hydrolysis to obtain the corresponding nano metal oxide Thing.
  • the nano metal oxide is selected from one or more of ZnO, NiO, W 2 O 3 , Mo 2 O 3 , TiO 2 , SnO, ZrO 2 and Ta 2 O 3 , but not Limited to this.
  • the composite material is oxidized with the initial nanometal
  • the molar mass ratio of the substance is related to the algebra of PAMAM dendrimers.
  • the PAMAM dendrimer in the composite material is the fifth generation PAMAM dendrimer
  • the molar ratio to the mass ratio of the initial nano metal oxide is 1 mmol: (1-50) mg, and the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the molar ratio of the sixth-generation PAMAM dendrimer to the mass of the nano metal oxide is 1 mmol: (10-150) mg
  • the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the molar ratio of the seventh generation PAMAM dendrimer to the mass of the nano metal oxide is 1 mmol: (50-250) mg
  • the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the molar ratio of the eighth generation PAMAM dendrimer to the mass of the nano metal oxide is 1 mmol: (100-250) mg
  • the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the molar ratio of the ninth-generation PAMAM dendrimer to the mass of the nano metal oxide is 1 mmol: (150-300) mg
  • the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the molar ratio of the molar amount of the tenth generation PAMAM dendrimer to the nano metal oxide is 1 mmol: (200-500) mg.
  • the composite material and the initial nano metal oxide are added to a polar solvent and mixed.
  • the PAMAM dendrimer is selected from one or both of the fifth generation PAMAM dendrimer and the sixth generation PAMAM dendrimer. Because the metal ions in the composite material will form a chemical bond with multiple N atoms in the gap of the terminal functional group of the PAMAM dendrimer, this makes the pyrolysis rate of the metal ion in the composite material slower than that of the organometallic precursor More; and the PAMAM dendrimers containing metal ions have larger corresponding viscosities as the algebraic number increases, and the greater the viscosity makes the coordination efficiency of the metal ions and oxygen vacancy coordination on the surface of the initial nano metal oxide decrease .
  • the PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer and the sixth generation One or two of PAMAM dendrimers.
  • the composite material and the nano metal oxide are added to a polar solvent, and the composite material and the initial nano metal oxide are stirred at 25-100° C. After ionization, the metal ions are combined with oxygen vacancies on the surface of the initial nano metal oxide to obtain a nano metal oxide.
  • the stirring speed is greater than 3000 rpm. In some embodiments, the stirring time is 0.5-3h.
  • the composite material and the nano metal oxide are added to a polar solvent, wherein the metal ion in the composite material and the metal ion in the nano metal oxide are the same element.
  • the metal ion coordinatedly bonded to the N atom in the gap of the terminal functional group of the PAMAM dendrimer in the composite material is Zn 2+ .
  • the metal ion in the composite material and the metal ion in the nano metal oxide are the same element, the metal ion can effectively eliminate the oxygen vacancy defects on the surface of the nano metal oxide, and can also effectively avoid other metal ions The combination of oxygen vacancies on the surface of the nano-metal oxide caused new surface defects.
  • the present disclosure also provides a nano metal oxide, which is prepared by the method of the present disclosure.
  • the present disclosure also provides a quantum dot light emitting diode including an electron transport layer, wherein the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure.
  • the nano metal oxide provided by the present disclosure has fewer surface defects, which can change the electron mobility of the nano metal oxide
  • the nano metal oxide prepared by the present disclosure having fewer surface defects is used as the electron of the quantum dot light emitting diode
  • the material of the transmission layer can adjust the electron mobility of the quantum dot light-emitting diode, so that the electron hole injection rate of the quantum dot light-emitting diode reaches a balance, thereby improving the luminous efficiency of the quantum dot light-emitting diode.
  • the quantum dot light emitting diode includes an anode, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode that are stacked, wherein the electron transport layer material is a nanometer prepared by the preparation method of the present disclosure Metal oxide.
  • 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.
  • QLED quantum dot light-emitting diode
  • the QLEDs can be divided into a QLED with a formal structure and a QLED with a flip structure.
  • the QLED of the formal structure includes an anode layered from the bottom up (the anode layered layer is disposed on the substrate), a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode ,
  • the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure.
  • the flip-chip QLED includes a cathode stacked from the bottom up (the cathode stack is disposed on the substrate), an electron transport layer, a quantum dot light emitting layer, a hole transport layer, and An anode, wherein the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure.
  • 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 material of the quantum dot light-emitting layer is selected from one or more of red quantum dots, green quantum dots, and blue quantum dots, and may also be selected from yellow light quantum dots.
  • the material of the quantum dot light emitting layer is selected from CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS , CuInSe, and one or more of various core-shell structure quantum dots or alloy structure quantum dots.
  • the quantum dots in the present disclosure may be selected from cadmium-containing or cadmium-free quantum dots.
  • the quantum dot light-emitting layer of the material has the characteristics of wide excitation spectrum and continuous distribution, and high stability of emission spectrum.
  • 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.
  • the present disclosure also provides a method for preparing a QLED with a hole-transporting layer in a formal structure, including the following steps:
  • the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure
  • a cathode is prepared on the electron transport layer to obtain QLED.
  • the present disclosure also provides a method for preparing a flip-chip structured QLED containing a hole transport layer, including the following steps:
  • the electron transport layer material is a nano metal oxide prepared by the preparation method of the present disclosure
  • An anode was prepared on the hole transport layer to obtain QLED.
  • 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
  • a quantum dot light-emitting diode comprising an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode stacked from bottom to top, wherein the electron transport layer material is Cu 2+ passivation Nano zinc oxide.
  • the preparation method of the quantum dot light-emitting diode includes the following steps:
  • nano-zinc oxide Disperse 0.5 mol of zinc acetate hydrate in 25 ml of dimethyl sulfoxide to make it completely dispersed to obtain the first mixed liquid; disperse 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of Completely disperse it in ethanol to obtain the second mixed liquid; after the first mixed liquid and the second mixed liquid are mixed and stirred at room temperature for 60 min, nano zinc oxide is prepared;
  • a 150 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to produce the quantum dot light-emitting diode.
  • a quantum dot light-emitting diode comprising an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode stacked from bottom to top, wherein the material of the electron transport layer is Zn 2+ passivation Nano zinc oxide.
  • the preparation method of the quantum dot light-emitting diode includes the following steps:
  • nano-zinc oxide Disperse 0.5 mol of zinc acetate hydrate in 25 ml of dimethyl sulfoxide to make it completely dispersed to obtain the first mixed liquid; disperse 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of Completely disperse it in ethanol to obtain the second mixed liquid; after the first mixed liquid and the second mixed liquid are mixed and stirred at room temperature for 60 min, nano zinc oxide is prepared;
  • Step 3 Preparation of Zn 2+ passivated nano-zinc oxide: taking 100 mg of nano-zinc oxide in step 2) dispersed in 100 ml of composite material in step 1), passivating treatment is carried out under the conditions of 60° C., speed 4000 rpm, time 30 min , Made Zn 2+ passivated nano-zinc oxide;
  • a 150 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to produce the quantum dot light-emitting diode.
  • a quantum dot light-emitting diode comprising an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode, which are stacked from bottom to top, wherein the material of the electron transport layer is Ag + passivated nano Nickel oxide.
  • the preparation method of the quantum dot light-emitting diode includes the following steps:
  • nano-nickel oxide Disperse 0.5 mol of nickel acetate hydrate in 25 ml of dimethyl sulfoxide to make it completely dispersed to obtain the first mixed liquid; disperse 0.55 mol of tetramethyl ammonium hydroxide in 30 ml of Completely disperse it in ethanol to obtain the second mixed liquid; after the first mixed liquid and the second mixed liquid are mixed and stirred at room temperature for 60 min, nano nickel oxide is prepared;
  • a 150 nm aluminum electrode is deposited on the electron transport layer through a mask plate by means of thermal steaming to produce the quantum dot light-emitting diode.
  • the present disclosure provides a method for preparing nano metal oxides, including the steps of providing a composite material including a PAMAM dendrimer and metal ions bound in the cavity of the PAMAM dendrimer Mixing the composite material with the initial nano-metal oxide in a polar solvent to coordinate the metal ions in the composite material with oxygen vacancies on the surface of the initial nano-metal oxide to obtain the nano-metal oxide.
  • the nano metal oxide with less surface defects can be prepared by the method of the present disclosure.
  • the electron mobility of the quantum dot light-emitting diode can be adjusted to make it electron
  • the hole injection rate reaches a balance, thereby improving its luminous efficiency.

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Abstract

一种纳米金属氧化物及其制备方法、量子点发光二极管，其中，所述纳米金属氧化物的制备方法包括步骤：提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。通过该方法能够制得表面缺陷较少的纳米金属氧化物，将所述纳米金属氧化物作为量子点发光二极管的电子传输层材料，可以调节量子点发光二极管的电子迁移率，从而使其电子空穴注入速率达到平衡，进而提高其发光效率。

Description

一种纳米金属氧化物及其制备方法、量子点发光二极管 技术领域
本公开涉及纳米金属氧化物钝化领域，尤其涉及一种纳米金属氧化物及其制备方法、量子点发光二极管。
背景技术
量子点发光二极管(QLED)的器件效率、寿命等技术指标的高低都与器件中的每一个功能层有着密切联系，其中，电子传输层影响着器件的电荷注入水平。金属氧化物纳米颗粒是用于量子点发光二极管的主要材料，金属氧化物纳米颗粒的电子迁移率和能带宽度对器件是影响器件的关键技术，因此制备具有合适电子迁移率和能带宽度的金属氧化物比较重要。
常规的合成方法制备得到的金属氧化物纳米颗粒表面存在较多的缺陷，其不仅会影响电子迁移率也会对QLED的其它功能层产生影响。
因此，相应的技术还有待于改进和发展。
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纳米金属氧化物的制备方法，旨在解决现有纳米金属氧化物表面存在较多缺陷的问题。
本公开的技术方案如下：
一种纳米金属氧化物的制备方法，其中，包括步骤：
提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。
一种纳米金属氧化物，其中，采用本公开方法制备而成。
一种量子点发光二极管，包括电子传输层，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物或本公开所述的纳米金属氧化物。
有益效果：本公开提供一种纳米金属氧化物的制备方法，通过利用腔体内结合有金属离子的PAMAM树形分子作为钝化前驱体，对初始纳米金属氧化物进行表面钝化处理可制得表面缺陷较少的纳米金属氧化物。
附图说明
图1为本公开一种纳米金属氧化物的制备方法较佳实施例的流程图。
具体实施方式
本公开提供一种纳米金属氧化物及其制备方法、量子点发光二极管，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。
请参阅图1，本公开提供一种纳米金属氧化物的制备方法较佳实施例的流程图，其中，如图所示，包括步骤：
S100、提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
S200、将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。
本实施例利用腔体内结合有金属离子的PAMAM树形分子作为钝化前驱体，对初始纳米金属氧化物进行表面钝化处理可制得表面缺陷较少的纳米金属氧化物。实现上述效果的机理具体如下：
由于常规制备的纳米金属氧化物表面存在较多的氧空位，将本公开提供的复合材料与所述纳米金属氧化物混合在极性溶剂环境中，所述复合材料中的金属离子会发生电离， 而表面存在氧空位的纳米金属氧化物在遇到游离的金属离子时比较容易产生化学配位作用，使游离的金属离子配位结合到纳米金属氧化物表面的氧空位中。因此，本实施例利用复合材料与初始纳米金属氧化物混合后，PAMAM树形分子中的金属离子电离后可配位结合在初始纳米金属氧化物的氧空位上，从而降低纳米金属氧化物表面的缺陷。
在一些实施方式中，所述复合材料的制备方法包括以下步骤：提供一种PAMAM树形分子；向金属离子溶液中加入所述PAMAM树形分子，混合使PAMAM树形分子腔体内的N原子与金属离子配位结合，得到复合材料。
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。
不同代数的PAMAM树形分子能够结合的金属离子的数量不同，其主要原因是不同代数的PAMAM树形分子能够配位金属离子的能力不同，当所述PAMAM树形分子的代数为第一代至第四代时，由于其末梢官能团(胺基)密集度较低，因此不易作为吸附金属离子的载体。
本实施例中，所述PAMAM树形分子选自第五代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。当所述PAMAM树形分子的代数为G5-G10时，由于其外围具有较多的官能团(胺基)且具有电负性，所述官能团与官能团之间通过产生静电相互作用能够形成完整而又封闭的空腔，因此G5-G10代的PAMAM树形分子可以作为制备与金属离子配位结合的候选材料。
在一些实施方式中，由于PAMAM树形分子为亲水性有机分子，且金属离子与所述PAMAM树形分子中的末梢官能团的N原子以配位键结合，因此，本实施例制备的所述复合材料能够稳定存放在极性溶剂中。在一些实施方式中，所述极性溶剂选自乙醇、水或甲醇中的一种。
在一些实施方式中，所述金属离子的元素类型选自Au、Ag、Cu、Fe、Ni、Zn和Mo中的一种或多种，但不限于此。
在一些实施方式中，按照预定比例将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。
本实施例中所述复合材料中的金属离子能够高效地与纳米金属氧化物表面的氧空位配位结合，而且不会引入其它不必要的阴离子影响纳米金属氧化物的钝化效果。
本实施例中，所述纳米金属氧化物的常规制备方法包括沉淀法、溶胶凝胶法以及微乳液法等，其中主要是采用溶胶凝胶法制备得到。所述溶胶凝胶法是指：将金属盐(如醋酸锌等)溶解在有机溶剂中(如乙醇)中，通过有机碱调节pH值并使所述金属盐水解制备，得到相应的纳米金属氧化物。
在一些实施方式中，所述纳米金属氧化物选自ZnO、NiO、W 2O 3、Mo 2O 3、TiO 2、SnO、ZrO 2和Ta 2O 3中的一种或多种，但不限于此。
在一些实施方式中，由于不同代数的PAMAM树形分子能够配位金属离子的能力不同，导致不同代数的PAMAM树形分子结合金属离子的量不同，因此所述复合材料与所述初始纳米金属氧化物的摩尔质量比与PAMAM树形分子的代数有关。以PAMAM树形分子配位结合金属离子的数量达到最大化为例，当所述复合材料中的PAMAM树形分子为第五代PAMAM树形分子时，按所述第五代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(1-50)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。当复合材料中的PAMAM树形分子为第六代PAMAM树形分子时，按所述第六代PAMAM树形分子的摩尔量与纳米金属氧化物的质量比为1mmol：(10-150)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。当复合 材料中的PAMAM树形分子为第七代PAMAM树形分子时，按所述第七代PAMAM树形分子的摩尔量与纳米金属氧化物的质量比为1mmol：(50-250)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。当复合材料中的PAMAM树形分子为第八代PAMAM树形分子时，按所述第八代PAMAM树形分子的摩尔量与纳米金属氧化物的质量比为1mmol：(100-250)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。当复合材料中的PAMAM树形分子为第九代PAMAM树形分子时，按所述第九代PAMAM树形分子的摩尔量与纳米金属氧化物的质量比为1mmol：(150-300)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。当复合材料中的PAMAM树形分子为第十代PAMAM树形分子时，按所述第十代PAMAM树形分子的摩尔量与纳米金属氧化物的质量比为1mmol：(200-500)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。
在一些实施方式中，所述PAMAM树形分子选自第五代PAMAM树形分子和第六代PAMAM树形分子中的一种或两种。由于复合材料中的金属离子会与PAMAM树形分子末梢官能团缝隙内的多个N原子产生化学键，这使得复合材料中金属离子的热解速率相比于有机金属前驱体的热解速率要缓慢得多；且所述含有金属离子的PAMAM树形分子随着代数的增大其相应的粘度也越大，粘度越大使得所述金属离子与初始纳米金属氧化物表面的氧空位配位结合效率降低。因此，本实施例为了保证复合材料中的金属离子能够更高效地与初始纳米金属氧化物表面的氧空位配位结合，所述PAMAM树形分子选自第五代PAMAM树形分子和第六代PAMAM树形分子中的一种或两种。
在一些实施方式中，将所述复合材料和纳米金属氧化物加入到极性溶剂中，在25-100℃的条件下对所述复合材料和初始纳米金属氧化物进行搅拌，使复合材料中的金属离子电离后与所述初始纳米金属氧化物表面的氧空位结合，得到纳米金属氧化物。在一些实施方式中，所述搅拌速度大于3000rpm。在一些实施方式中，所述搅拌时间为0.5-3h。
在一些实施方式中，将所述复合材料和纳米金属氧化物加入到极性溶剂中，其中，所述复合材料中的金属离子与所述纳米金属氧化物中的金属离子为相同元素。作为举例， 当所述初始纳米金属氧化物为氧化锌时，则所述复合材料中与PAMAM树形分子末梢官能团缝隙内N原子配位结合的金属离子为Zn 2+。当所述复合材料中的金属离子与所述纳米金属氧化物中的金属离子为相同元素时，所述金属离子既能够有效消除纳米金属氧化物表面的氧空位缺陷，又能够有效避免其它金属离子结合在纳米金属氧化物表面氧空位后又造成新的表面缺陷。
本公开还提供一种纳米金属氧化物，其中，采用本公开方法制备而成。
本公开还提供一种量子点发光二极管，包括电子传输层，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物。
由于本公开提供的纳米金属氧化物表面缺陷较少，其能够改变纳米金属氧化物的电子迁移率，因此，将本公开制得的表面缺陷较少的纳米金属氧化物作为量子点发光二极管的电子传输层材料，可以调节量子点发光二极管的电子迁移率，从而使量子点发光二极管的电子空穴注入速率达到平衡，进而提高量子点发光二极管的发光效率。
在一些实施方式中，所述量子点发光二极管包括层叠设置的阳极、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物。
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。
下面对含空穴传输层的量子点发光二极管(QLED)结构及其制备方法作详细说明：
根据所述QLED发光类型的不同，所述QLED可以分为正装结构的QLED和倒装结构的QLED。
在一些实施方式中，所述正装结构的QLED包括从下往上叠层设置的阳极(所述阳极叠层设置于衬底上)、空穴传输层、量子点发光层、电子传输层和阴极，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物。
在一些实施方式中，所述倒装结构的QLED包括从下往上叠层设置的阴极(所述阴极叠层设置于衬底上)、电子传输层、量子点发光层、空穴传输层和阳极，其中，所述 电子传输层材料为本公开制备方法制备的纳米金属氧化物。
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，所述量子点发光层的材料选自红量子点、绿量子点、蓝量子点中的一种或多种，也可选自黄光量子点。具体的，所述量子点发光层的材料选自CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、以及各种核壳结构量子点或合金结构量子点中的一种或多种。本公开所述量子点可以选自含镉或者不含镉量子点。该材料的量子点发光层具有激发光谱宽并且连续分布，发射光谱稳定性高等特点。
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。
本公开还提供一种正装结构的含空穴传输层的QLED的制备方法，包括如下步骤：
提供含阳极的衬底，在阳极上制备空穴传输层；
在空穴传输层上制备量子点发光层；
在量子点发光层上制备电子传输层，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物；
在电子传输层上制备阴极，得到QLED。
本公开还提供一种倒装结构的含空穴传输层的QLED的制备方法，包括如下步骤：
提供含有阴极的衬底，在所述阴极上制备电子传输层，其中，所述电子传输层材料为本公开制备方法制备的纳米金属氧化物；
在电子传输层上制备量子点发光层；
在量子点发光层上制备空穴传输层；
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。
下面通过实施例对本公开量子点发光二极管及其制备方法进行详细说明：
实施例1
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层材料为Cu 2+钝化纳米氧化锌。所述量子点发光二极管的制备方法包括步骤：
1)、复合材料的制备：将第五代PAMAM树形分子水溶液(1×10 -2mol/L)与Cu(NO 3) 2水溶液(1.0×10 -2mol/L)加入装有搅拌装置的反应器中，室温搅拌2h制备得到含有Cu 2+的PAMAM树形分子(G5)溶液(1×10 -2mol/L)备用；
2)、纳米氧化锌的制备：将0.5mol的水合醋酸锌分散在25ml的二甲基亚砜中使其 完全分散得到第一混合液；将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散得到第二混合液；将第一混合液和第二混合液进行室温混合搅拌60min后，制得纳米氧化锌；
3)、Cu 2+钝化纳米氧化锌的制备：取步骤2)中纳米氧化锌40mg分散在步骤1)中的100ml复合材料中，采用50℃、转速5000rpm、时间30min的条件进行钝化处理，制得Cu 2+钝化纳米氧化锌；
4)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂PVK，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤3)中制得的Cu 2+钝化纳米氧化锌，旋涂60s后以120℃退火处理30min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积150nm的铝电极，制得所述量子点发光二极管。
实施例2
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层材料为Zn 2+钝化纳米氧化锌。所述量子点发光二极管的制备方法包括步骤：
1)、复合材料的制备：将第六代PAMAM树形分子水溶液(1×10 -2mol/L)与Zn(NO 3) 2水溶液(1.0×10 -2mol/L)加入装有搅拌装置的反应器中，室温搅拌2h制备得到含有Zn 2+的PAMAM树形分子(G6)溶液(1×10 -2mol/L)备用；
2)、纳米氧化锌的制备：将0.5mol的水合醋酸锌分散在25ml的二甲基亚砜中使其完全分散得到第一混合液；将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散得到第二混合液；将第一混合液和第二混合液进行室温混合搅拌60min后，制得纳米氧化锌；
3)、Zn 2+钝化纳米氧化锌的制备：取步骤2)中纳米氧化锌100mg分散在步骤1)中的100ml复合材料中，采用60℃、转速4000rpm、时间30min的条件进行钝化处理，制得Zn 2+钝化纳米氧化锌；
4)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂TFB，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤3)中制得的Zn 2+钝化纳米氧化锌，旋涂60s后以100℃退火处理40min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积150nm的铝电极，制得所述量子点发光二极管。
实施例3
一种量子点发光二极管，其包括从下至上叠层设置的阳极衬底、空穴传输层、量子点发光层、电子传输层以及阴极，其中，所述电子传输层材料为Ag +钝化纳米氧化镍。所述量子点发光二极管的制备方法包括步骤：
1)、复合材料的制备：将第八代PAMAM树形分子水溶液(1×10 -2mol/L)与AgNO 3水溶液(1.0×10 -2mol/L)加入装有搅拌装置的反应器中，室温搅拌2h制备得到含有Ag +的PAMAM树形分子(G8)溶液(1×10 -2mol/L)备用；
2)、纳米氧化镍的制备：将0.5mol的水合醋酸镍分散在25ml的二甲基亚砜中使其完全分散得到第一混合液；将0.55mol的四甲基氢氧化铵分散在30ml的乙醇中使其完全分散得到第二混合液；将第一混合液和第二混合液进行室温混合搅拌60min后，制得纳米氧化镍；
3)、Ag +钝化纳米氧化镍的制备：取步骤2)中纳米氧化锌150mg分散在步骤1)中的100ml复合材料中，采用80℃、转速6000rpm、时间30min的条件进行钝化处理，制得Ag +钝化纳米氧化镍；
4)、量子点发光二极管的制备：
以4000rpm的转速在清洗干净的ITO玻璃片上旋涂PVK，旋涂60s后以150℃退火处理15min，制得空穴传输层；
以2000rpm的转速在空穴传输层上旋涂红色量子点CdSe/ZnS溶液，旋涂60s后制得量子点发光层；
以3000rpm的转速在量子点发光层上旋涂所述步骤3)中制得的Ag +钝化纳米氧化镍，旋涂60s后以120℃退火处理30min，制得电子传输层；
最后，在所述电子传输层上通过掩膜板采用热蒸的方式沉积150nm的铝电极，制得所述量子点发光二极管。
综上所述，本公开提供一种纳米金属氧化物的制备方法，包括步骤：提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。通过本公开方法能够制得表面缺陷较少的纳米金属氧化物，将所述纳米金属氧化物作为量子点发光二极管的电子传输层材料，可以调节量子点发光二极管的电子迁移率，从而使其电子空穴注入速率达到平衡，进而提高其发光效率。
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. 一种纳米金属氧化物的制备方法，其特征在于，包括步骤：
    提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
    将所述复合材料和初始纳米金属氧化物在极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。
  2. 根据权利要求1所述纳米金属氧化物的制备方法，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。
  3. 根据权利要求1所述纳米金属氧化物的制备方法，其特征在于，所述所述PAMAM树形分子选自第五代和第六代PAMAM树形分子中的一种或两种。
  4. 根据权利要求1所述纳米金属氧化物的制备方法，其特征在于，所述金属离子的元素种类选自Au、Ag、Cu、Fe、Ni、Zn和Mo中的一种或多种。
  5. 根据权利要求1所述纳米金属氧化物的制备方法，其特征在于，所述纳米金属氧化物选自ZnO、NiO、W 2O 3、Mo 2O 3、TiO 2、SnO、ZrO 2和Ta 2O 3中的一种或多种。
  6. 根据权利要求1所述纳米金属氧化物的制备方法，其特征在于，所述复合材料中的金属离子与所述初始纳米金属氧化物中的金属离子为相同元素。
  7. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第五代PAMAM树形分子时，按所述第五代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(1-50)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。
  8. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第六代PAMAM树形分子时，按所述第六代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(10-150)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。
  9. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第七代PAMAM树形分子时，按所述第七代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(50-250)mg，将所述复合材料和 初始纳米金属氧化物加入到极性溶剂中混合。
  10. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第八代PAMAM树形分子时，按所述第八代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(100-250)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合；
  11. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第九代PAMAM树形分子时，按所述第九代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(150-300)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。
  12. 根据权利要求2所述纳米金属氧化物的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第十代PAMAM树形分子时，按所述第十代PAMAM树形分子的摩尔量与初始纳米金属氧化物的质量比为1mmol：(200-500)mg，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合。
  13. 根据权利要求7所述纳米金属氧化物的制备方法，其特征在于，在25-100℃条件下，将所述复合材料和初始纳米金属氧化物加入到极性溶剂中混合，使复合材料中的金属离子电离后与初始纳米金属氧化物表面的氧空位配位结合，得到所述纳米金属氧化物。
  14. 一种纳米金属氧化物，其特征在于，采用权利要求1-13任意一种方法制备而成。
  15. 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所述阳极之间的量子点发光层，所述阴极和所述量子点发光层之间设置有电子传输层，其特征在于，所述电子传输层材料为权利要求1-13任一所述制备方法制备的纳米金属氧化物或权利要求14所述的纳米金属氧化物。
  16. 根据权利要求15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设置有空穴传输层。
  17. 根据权利要求16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。
  18. 根据权利要求15所述的量子点发光二极管，其特征在于，所述阳极的材料选自ITO、FTO、ATO、AZO、GZO、IZO、MZO和AMO中的一种或多种。
  19. 根据权利要求15所述的量子点发光二极管，其特征在于，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。
  20. 根据权利要求15所述的量子点发光二极管，其特征在于，所述量子点发光层材料选自红量子点、绿量子点、蓝量子点中的一种或多种。
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