WO2022199037A1 - 氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法 - Google Patents

氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法 Download PDF

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WO2022199037A1
WO2022199037A1 PCT/CN2021/129006 CN2021129006W WO2022199037A1 WO 2022199037 A1 WO2022199037 A1 WO 2022199037A1 CN 2021129006 W CN2021129006 W CN 2021129006W WO 2022199037 A1 WO2022199037 A1 WO 2022199037A1
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zinc oxide
oxide nanoparticle
solution
nanoparticle solution
preparing
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French (fr)
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马兴远
徐威
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TCL Technology Group Co Ltd
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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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • 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
    • 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
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the application relates to the technical field of nanomaterials, in particular to a method for preparing a zinc oxide nanoparticle solution, a method for preparing a zinc oxide film, and a method for preparing a quantum dot light-emitting diode.
  • Quantum dots have become a research hotspot in next-generation display technology due to their tunable wavelengths, high color saturation, high material stability, and low fabrication costs.
  • quantum dot light-emitting diodes Quantum Dot Light Emitting The external quantum efficiency of Diode, QLED
  • QLED Quantum Dot Light Emitting
  • organic light-emitting diodes Organic Light-Emitting Diodes. Diode, OLED).
  • the device structure of QLED is similar to that of OLED, and it has a sandwich structure similar to p-i-n junction. By balancing the injection of electrons and holes, it achieves the effect of efficient light emission.
  • Zinc oxide is often used as an electron transport layer material, and there is a charge transfer phenomenon between the interface between zinc oxide and the quantum dot light-emitting layer, especially in blue QLED devices; the transfer of excited electrons between the interfaces not only leads to the accumulation of charges at the interface, but also improves the Probability of radiative Auger recombination.
  • the complex interaction between the QD light-emitting layer and the ZnO electron transport layer is closely related to the oxygen vacancy concentration, conduction band position and electron transport rate of ZnO, which will change during the storage and aging of the device. Therefore, the stability of ZnO is critical to the efficiency and lifetime of the device.
  • the purpose of the embodiments of the present application is to provide a method for preparing a zinc oxide nanoparticle solution, a method for preparing a zinc oxide film, and a method for preparing a quantum dot light-emitting diode.
  • a first aspect provides a method for preparing a zinc oxide nanoparticle solution, comprising the following steps:
  • a metal acetate solution is added to the initial zinc oxide nanoparticle solution to obtain the zinc oxide nanoparticle solution.
  • a method for preparing a zinc oxide film comprising the steps of:
  • the zinc oxide nanoparticle solution is spin-coated on a substrate, and then heat-treated to obtain the zinc oxide thin film.
  • a method for preparing a quantum dot light-emitting diode comprising the following steps:
  • the zinc oxide nanoparticle solution is spin-coated on the substrate, followed by heat treatment to obtain an electron transport layer.
  • the beneficial effect of the preparation method of the zinc oxide nanoparticle solution provided by the embodiments of the present application is that the present application adds the metal acetate solution to the initial zinc oxide nanoparticle solution and mixes to obtain the final zinc oxide nanoparticle solution.
  • the carboxyl group can replace part of the hydroxyl groups on the surface of the initial zinc oxide nanoparticles, passivate the surface defects of the zinc oxide nanoparticles, and the carboxyl group has a strong binding force with the zinc oxide nanoparticles, and has higher solubility, thereby improving the solution of the zinc oxide nanoparticles. storage stability in .
  • the beneficial effect of the method for preparing the zinc oxide thin film is that the present application adds the metal acetate solution into the initial zinc oxide nanoparticle solution and mixes to obtain the zinc oxide nanoparticle solution, and then spin-coating on the substrate to form a film to prepare the oxide
  • the zinc oxide nanoparticle solution used for film formation is added with a metal acetate solution, so that the zinc oxide thin film with good stability can be prepared.
  • the beneficial effect of the method for preparing a quantum dot light-emitting diode is that the present application adds a metal acetate solution to an initial zinc oxide nanoparticle solution and mixes to obtain a zinc oxide nanoparticle solution, and then spin-coats the substrate to form a film to form a solution.
  • the zinc oxide thin film is the electron transport layer, and the zinc oxide nanoparticle solution used for spin coating is added with a metal acetate solution, which makes the electron transport layer after film formation have good stability, thus improving the final preparation.
  • Luminous efficiency and lifetime of quantum dot light-emitting diode devices are examples of quantum dot light-emitting diode devices.
  • Fig. 1 is the schematic flow sheet of the preparation method of the zinc oxide nanoparticle solution provided in the embodiment of the present application;
  • FIG. 2 is a schematic flowchart of a method for preparing a zinc oxide film provided in an embodiment of the present application
  • FIG. 3 is a schematic flowchart of a method for preparing a quantum dot light-emitting diode provided by an embodiment of the present application
  • FIG. 4 is a schematic structural diagram of a quantum dot light-emitting diode provided by an embodiment of the present application.
  • At least one refers to one or more, and “multiple” refers to two or more.
  • At least one item(s) below” or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items(s).
  • Some embodiments of the present application provide a method for preparing a zinc oxide nanoparticle solution, as shown in FIG. 1 , the preparation method includes the following steps:
  • the metal acetate salt solution is added to the initial zinc oxide nanoparticle solution and mixed, so that the metal acetate salt in the solution will modify the initial zinc oxide nanoparticles. Specifically, After the dissolution of the metal acetate salt, the carboxyl group will replace some of the hydroxyl groups on the surface of the initial zinc oxide nanoparticles, thereby passivating the surface defects of the zinc oxide nanoparticles.
  • the obtained zinc oxide nanoparticle solution is not easy to agglomerate during storage, and has good stability.
  • the zinc oxide nanoparticle solution prepared in the examples of this application is prepared into a zinc oxide film, and when used as an electron transport layer of a light-emitting device, such as a quantum dot light-emitting diode device, the stability of the light-emitting device can be improved, thereby improving the luminous efficiency of the light-emitting device. and service life.
  • a light-emitting device such as a quantum dot light-emitting diode device
  • the provided initial zinc oxide nanoparticle solution is a solution containing initial zinc oxide nanoparticles, which can either be a solution obtained by dissolving the initial zinc oxide nanoparticles purchased in the market directly in a solvent, or directly using the solution.
  • the solvent in the initial zinc oxide nanoparticle solution can be an alcohol solvent, such as methanol, ethanol, propanol, etc., and the alcohol solvent can be used to disperse the zinc oxide nanoparticles.
  • the initial zinc oxide nanoparticle concentration in the initial zinc oxide nanoparticle solution is 10-60 mg/mL, such as 10 mg/mL, 15 mg/mL, 20 mg/mL, 30 mg/mL, 40 mg/mL, 50 mg/mL mL, 60mg/mL, etc.
  • the initial zinc oxide nanoparticles are uniformly dispersed and can fully react with the acetate solution.
  • the metal acetate salt solution is added to the initial zinc oxide nanoparticle solution and mixed, so that the metal acetate salt in the solution will modify the initial zinc oxide nanoparticles.
  • the concentration of acetate metal salt can be 10 ⁇ 30mg/mL, such as 10mg/mL, 15mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, etc., within the above concentration range, acetate metal salt The metal acetate salt in the solution is uniformly dispersed.
  • the molar ratio of zinc ions in the initial zinc oxide nanoparticle solution to metal acetate in the metal acetate solution is (2 ⁇ 10):1, such as 2:1, 4:1, 5:1 , 6:1, 8:1, 10:1, etc.
  • the metal acetate salt can well modify the ZnO nanoparticles without excessively depleting the material.
  • the acetate metal salt in the acetate metal salt solution includes but is not limited to at least one of magnesium acetate, aluminum acetate, sodium acetate, potassium acetate and zinc acetate, for example, it can be one of the above-mentioned metal acetate salts , or a combination of two or more of the above metal acetate salts.
  • the metal ions in the above-mentioned metal acetate salts are not zinc ions (for example, are magnesium ions, aluminum ions, potassium ions or sodium ions), so that part of the zinc ions on the surface of the initial zinc oxide nanoparticles can be replaced, so that zinc oxide can be replaced.
  • the electronic structure of ZnO can be adjusted to a certain extent to optimize the electrical properties of ZnO.
  • the zinc oxide nanoparticle solution thus obtained is not only difficult to agglomerate during storage and has good stability, but also the electrical properties of the zinc oxide nanoparticle are improved.
  • the method for preparing the zinc oxide nanoparticle solution further includes: after adding the metal acetate salt solution to the initial zinc oxide nanoparticle solution, using ethanol and/or ethyl acetate to clean the initial solution after adding the metal acetate salt solution zinc oxide nanoparticle solution, and dissolving the cleaned zinc oxide nanoparticle in an alcohol solvent to obtain a zinc oxide nanoparticle solution.
  • the carboxyl group in the metal acetate salt can passivate the surface defects of the zinc oxide nanoparticles well, improve the stability of the zinc oxide nanoparticles, and make the zinc oxide nanoparticle solution difficult to agglomerate during the storage process.
  • the zinc nanoparticle solution is used for film formation, and a zinc oxide film with good stability can be obtained.
  • the electron transport layer of the quantum dot light-emitting diode also improves the stability of zinc oxide in the device.
  • the solvent in the metal acetate salt solution is an alcohol solvent
  • the solvent in the initial zinc oxide nanoparticle solution is the same or a different alcohol solvent, mixed in an alcohol solvent system, and has good stability and does not affect the metal acetate salt Modification of pristine zinc oxide nanoparticles.
  • the above-mentioned alcohol solvent is selected from at least one of methanol, ethanol and propanol.
  • the alcohol solvent in the metal acetate salt solution, the alcohol solvent in the initial zinc oxide nanoparticle solution and the alcohol solvent dissolved in the cleaned zinc oxide nanoparticles can be selected from the same single-component alcohol solvent, or different single-component alcohols
  • the solvent, or two of them are selected from the same one-component alcohol solvent, the other is a different one-component alcohol solvent, or any combination of the same or different alcohol solvents.
  • the alcohol solvent can not only disperse the zinc oxide nanoparticles well, but also dissolve the metal acetate salt. In the alcohol solvent system, the metal acetate salt can fully modify the surface of the initial zinc oxide nanoparticles, and finally obtain a stable zinc oxide nanoparticle solution. .
  • Some embodiments of the present application provide a method for preparing a zinc oxide film, as shown in FIG. 2 , the preparation method includes the following steps:
  • E01 providing an initial zinc oxide nanoparticle solution, adding a metal acetate solution to the initial zinc oxide nanoparticle solution to obtain a zinc oxide nanoparticle solution;
  • E02 The zinc oxide nanoparticle solution is spin-coated on the substrate, followed by heat treatment to obtain a zinc oxide thin film.
  • the preparation method of the zinc oxide film provided by the embodiment of the present application uses the zinc oxide nanoparticle solution obtained by the above-mentioned unique preparation method of the zinc oxide nanoparticle solution of the present application for spin coating, because the zinc oxide nanoparticle solution used for film formation is used for spin coating.
  • a metal acetate solution is added to the solution, so that a zinc oxide film with good stability can be prepared.
  • the stable zinc oxide film can be used as the electron transport layer of the quantum dot light-emitting diode, which can improve the stability of the device and has a good prospect. .
  • the above-mentioned step E01 is the preparation process of the zinc oxide nanoparticle solution.
  • the zinc oxide nanoparticle solution used for film formation in the examples of the present application is the zinc oxide nanoparticle solution obtained by the aforementioned preparation method of the zinc oxide nanoparticle solution, the concentration and solvent type of the aforementioned initial zinc oxide nanoparticle solution, the metal acetate The concentration of the salt solution, the type of metal acetate salt and the type of solvent, as well as the related molar ratios and cleaning steps, etc. can all be used in step E01. Therefore, the zinc oxide nanoparticle solution prepared in the above-mentioned step E01 has all the advantages of the alternative solutions provided by the preparation method of the zinc oxide nanoparticle solution in the above-mentioned embodiment, and will not be repeated here.
  • the above-mentioned step E02 is the zinc oxide nanoparticle solution film forming process, wherein the temperature of the heating treatment can be 60 ⁇ 100°C, such as 600°C, 70°C, 90°C, 100°C, etc., and the time of the heating treatment can be 10 ⁇ 30min, Such as 10min, 15min, 20min, 25min, etc. Under the above conditions, the solvent can be evaporated better and a stable zinc oxide film can be formed.
  • Some embodiments of the present application also provide a preparation method of a quantum dot light-emitting diode, as shown in FIG. 3 , the preparation method includes the following steps:
  • T01 Provide substrate
  • T02 providing an initial zinc oxide nanoparticle solution, adding a metal acetate solution to the initial zinc oxide nanoparticle solution to obtain a zinc oxide nanoparticle solution;
  • T03 spin-coating the zinc oxide nanoparticle solution on the substrate, followed by heat treatment, to obtain an electron transport layer.
  • the stability of zinc oxide has a great influence on the performance of the device, which can be divided into the storage stability of zinc oxide solution and the effect of zinc oxide on the stability of the device.
  • the initial zinc oxide nanoparticle solution is modified with metal acetate, the carboxyl group will replace part of the hydroxyl group on the surface of the zinc oxide nanoparticle, the carboxyl group has a strong binding force with the zinc oxide nanoparticle, and has a higher solubility
  • the carboxyl group is more stable than the hydroxyl group, which can better passivate the surface defects of zinc oxide, eliminate the defect energy level of zinc oxide, and reduce the emission layer and electron transport layer of quantum dots.
  • the fluorescence quenching at the interface improves the luminous efficiency of the device. Therefore, the luminous efficiency and service life of the prepared quantum dot light-emitting diode device are finally improved by the preparation method.
  • the metal acetate salt in the acetate metal salt solution can be selected from at least one of magnesium acetate, aluminum acetate, sodium acetate, potassium acetate and zinc acetate.
  • magnesium acetate is used as the metal acetate salt, or it can be Using sodium acetate and zinc acetate, or using aluminum acetate, sodium acetate and potassium acetate at the same time, in this way, after adding the metal acetate salt solution to the initial zinc oxide nanoparticle solution, the metal ions in the acetate metal salt such as sodium ion, potassium ion, Aluminum ions or magnesium ions can replace zinc ions on the surface of zinc oxide, adjust the electronic structure of zinc oxide nanoparticles to a certain extent, and optimize the electrical properties of zinc oxide, thereby improving the light-emitting performance of quantum dot light-emitting diodes.
  • the provided substrate may be a substrate with various functional layers deposited on the surface.
  • the quantum dot light-emitting diode is an upright device
  • the preparation method may include the following steps: providing a substrate, an anode is prepared on the surface of the substrate, and a quantum dot light-emitting layer is prepared on the anode; Preparation method: A zinc oxide film is prepared on the surface of the quantum dot light-emitting layer on a substrate to obtain an electron transport layer; then a cathode is prepared on the electron transport layer.
  • a hole functional layer (such as preparing a hole transport layer, or sequentially preparing a stacked hole injection layer and a hole transport layer) can be prepared on the anode, and then on the anode.
  • the quantum dot light-emitting layer is prepared on the hole functional layer.
  • the electron injection layer may be prepared on the electron transport layer first, and then the anode may be prepared on the electron injection layer.
  • the quantum dot light-emitting diode is an inverted device, and the preparation method thereof may include the following steps: providing a substrate, and a cathode is prepared on the substrate; preparing the surface of the cathode on the substrate by using the preparation method of the zinc oxide film described above in the present application A zinc oxide film is obtained to obtain an electron transport layer; a quantum dot light-emitting layer is prepared on the electron transport layer; an anode is prepared on the quantum dot light-emitting layer.
  • a hole functional layer can be prepared on the quantum dot light-emitting layer (for example, preparing a hole transport layer, or preparing a stacked hole transport layer and a hole injection layer in turn), The anode is then prepared on the hole functional layer.
  • the electron injection layer may be prepared on the cathode first, and then the electron transport layer may be prepared on the electron injection layer.
  • the above step T02 is the preparation process of the zinc oxide nanoparticle solution for preparing the electron transport layer.
  • the zinc oxide nanoparticle solution used to make the electron transport layer in the examples of the present application is the zinc oxide nanoparticle solution obtained by the aforementioned preparation method of the zinc oxide nanoparticle solution, and the aforementioned concentration and solvent type of the initial zinc oxide nanoparticle solution , the concentration of the acetate metal salt solution, the type of the metal acetate salt and the solvent, and the relevant molar ratios and cleaning steps can all be used in step T02. Therefore, the zinc oxide nanoparticle solution prepared in the above step T02 has all the advantages of the alternative solutions provided by the preparation method of the zinc oxide nanoparticle solution in the above-mentioned embodiment, and details are not repeated here.
  • the above-mentioned step T03 is the process of forming a film of zinc oxide nanoparticle solution to form an electron transport layer, wherein the temperature of the heating treatment can be 60-100 °C, such as 600 °C, 70 °C, 90 °C, 100 °C, etc., and the time of the heating treatment can be It is 10 ⁇ 30min, such as 10min, 15min, 20min, 25min, etc. Under the above conditions, the solvent can be evaporated better and a stable electron transport layer can be formed.
  • the embodiment of the present application further provides a quantum dot light-emitting diode, which is prepared by the above-mentioned preparation method of a quantum dot light-emitting diode.
  • the device has good luminous efficiency and service life.
  • the quantum dot light-emitting diode includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode, an electron transport layer is disposed between the cathode and the quantum dot light-emitting layer, and the electron transport layer is the embodiment of the application.
  • the zinc oxide film obtained by the method for preparing the zinc oxide film is provided.
  • an electron injection layer may also be disposed between the electron transport layer and the cathode of the quantum dot light-emitting diode.
  • a hole transport layer may also be provided between the anode and the quantum dot light-emitting layer.
  • a hole injection layer may be provided between the anode and the hole transport layer.
  • the preparation of zinc oxide nanoparticle solution includes the following steps
  • the preparation of zinc oxide film includes the following steps:
  • the preparation of quantum dot light-emitting diodes includes the following steps:
  • the zinc oxide nanoparticle solution prepared in Example 1 (the mass concentration of zinc oxide was 30 mg/mL) was directly spin-coated at a rotational speed of 3000 rpm for 30 s, and then heated at 80 ° C for 20 min. The steps are performed in a glove box.
  • the preparation of quantum dot light-emitting diodes includes the following steps:
  • Example 1 After storing the zinc oxide nanoparticle solution prepared in Example 1 (the mass concentration of zinc oxide is 30 mg/mL) in a refrigerator at 5 °C for 14 days, spin-coating was performed at a rotational speed of 3000 rpm, and the spin-coating time was 30 s. It was then heated at 80° C. for 20 min, which was carried out in a glove box.
  • a quantum dot light-emitting diode as shown in Figure 4, from bottom to top: substrate 10, anode 1, hole injection layer 2, hole transport layer 3, quantum dot light-emitting layer 4, electron transport layer 5, cathode 6 .
  • the device was prepared using the procedure of Example 3.
  • a quantum dot light-emitting diode as shown in Figure 4, from bottom to top: substrate 10, anode 1, hole injection layer 2, hole transport layer 3, quantum dot light-emitting layer 4, electron transport layer 5, cathode 6 .
  • the device was prepared using the procedure of Example 4.
  • a quantum dot light-emitting diode as shown in Figure 4, from bottom to top: substrate 10, anode 1, hole injection layer 2, hole transport layer 3, quantum dot light-emitting layer 4, electron transport layer 5, cathode 6 .
  • Example 3 In the preparation steps of the device, other steps are the same as those in Example 3, except that the electron transport layer was prepared using the unmodified initial zinc oxide nanoparticle ethanol solution (the prepared zinc oxide mass concentration was 30 mg/mL) in Example 1. .
  • Example 1 Test the particle size of the zinc oxide nanoparticle solution prepared in Example 1.
  • the specific test method is as follows: the zinc oxide nanoparticle solution is tested by the scattering method with a laser particle size distribution tester to obtain the particle size, and the results are shown in the table. 1 shows:
  • the zinc oxide nanoparticle solution prepared in Example 1 Zinc oxide nanoparticles particle size Just finished the preparation step 5.0nm Store in a 5°C refrigerator for 14 days after the preparation step 5.1nm
  • T95 1000nit refers to the time it takes for the brightness to decay from 1000nit to 95%.
  • the preparation method of the zinc oxide nanoparticle solution of the embodiments of the present application can significantly improve the storage stability of the zinc oxide nanoparticle solution, and this type of zinc oxide nanoparticle solution is used to prepare quantum dot luminescence
  • the electron transport layer of the diode can improve the luminous efficiency and service life of the device.

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Abstract

本申请公开一种氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法。该氧化锌纳米颗粒溶液的制备方法包括提供初始氧化锌纳米颗粒溶液，向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液。将该制备方法得到的氧化锌纳米颗粒溶液旋涂成膜用作发光器件的电子传输层。

Description

氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法
本申请要求于2021年03月22日在中国专利局提交的、申请号为202110301125.8、申请名称为“氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法、量子点发光二极管及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及纳米材料技术领域，具体涉及一种氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法。
 背景技术
量子点（Quantum Dot，QD）因其波长可调、色彩饱和度高、材料稳定性高、制备成本低廉等优点，成为了下一代显示技术的研究热点。经过了将近二十几年的发展，量子点发光二极管（Quantum Dot Light Emitting Diode，QLED）的外量子效率已经得到一定的提升，从器件效率方面，量子点发光二极管已经相当接近有机发光二极管（Organic Light-Emitting Diode，OLED）。
目前QLED的器件结构与OLED相似，具有类似p-i-n结的三明治结构，通过平衡电子和空穴的注入，达到高效发光的效果。氧化锌常用作电子传输层材料，氧化锌与量子点发光层的界面间存在电荷转移现象，特别是蓝色QLED器件；界面间激发电子的转移不仅导致了界面处的电荷积累，而且提高了非辐射俄歇复合的概率。
量子点发光层和氧化锌电子传输层之间复杂的相互作用与氧化锌的氧空位浓度、导带位置和电子传输率密切相关，这些在器件的储存老化过程中会发生一定变化。因此，氧化锌的稳定性对器件的效率和寿命很关键。
 技术问题
本申请实施例的目的在于提供一种氧化锌纳米颗粒溶液的制备方法、氧化锌薄膜的制备方法和量子点发光二极管的制备方法。
 技术解决方案
本申请实施例采用的技术方案是：
第一方面，提供一种氧化锌纳米颗粒溶液的制备方法，包括如下步骤：
提供初始氧化锌纳米颗粒溶液；
向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到所述氧化锌纳米颗粒溶液。
第二方面，提供一种氧化锌薄膜的制备方法，包括如下步骤：
提供初始氧化锌纳米颗粒溶液，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
将所述氧化锌纳米颗粒溶液旋涂在基板上，随后进行加热处理，得到所述氧化锌薄膜。
第三方面，提供一种量子点发光二极管的制备方法，包括如下步骤：
提供基板；
提供初始氧化锌纳米颗粒溶液，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
将所述氧化锌纳米颗粒溶液旋涂在所述基板上，随后进行加热处理，得到电子传输层。
 有益效果
本申请实施例提供的氧化锌纳米颗粒溶液的制备方法的有益效果在于本申请将醋酸金属盐溶液加入到初始氧化锌纳米颗粒溶液中混合得到最终的氧化锌纳米颗粒溶液，醋酸金属盐溶解后的羧基可以取代初始氧化锌纳米颗粒表面的部分羟基，钝化氧化锌纳米颗粒表面缺陷，而且羧基与氧化锌纳米颗粒的结合力强，具有更高的溶解性，从而提高了氧化锌纳米颗粒在溶液中的存放稳定性。
本申请实施例提供的氧化锌薄膜的制备方法的有益效果在于本申请将醋酸金属盐溶液加入到初始氧化锌纳米颗粒溶液中混合得到氧化锌纳米颗粒溶液后，在基板上旋涂成膜制备氧化锌薄膜，因该用于成膜的氧化锌纳米颗粒溶液中加入有醋酸金属盐溶液，从而可以制备得到稳定性好的氧化锌薄膜。
本申请实施例提供的量子点发光二极管的制备方法的有益效果在于本申请将醋酸金属盐溶液加入到初始氧化锌纳米颗粒溶液中混合得到氧化锌纳米颗粒溶液，然后在基板上旋涂成膜形成的氧化锌薄膜即为电子传输层，用于旋涂的氧化锌纳米颗粒溶液中加入有醋酸金属盐溶液，使得成膜后的电子传输层具有很好的稳定性，因而提高了最终制得的量子点发光二极管器件的发光效率和使用寿命。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1是本申请实施例提供的氧化锌纳米颗粒溶液的制备方法流程示意图；
图2是本申请实施例提供的氧化锌薄膜的制备方法流程示意图；
图3是本申请实施例提供的量子点发光二极管的制备方法流程示意图；
图4是本申请实施例提供的量子点发光二极管的结构示意图。
 本发明的实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一种”是指一种或者多种，“多种”是指两种或两种以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项（个）或复数项（个）的任意组合。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
为了说明本申请所提供的技术方案，以下结合具体附图及实施例进行详细说明。
本申请一些实施例提供一种氧化锌纳米颗粒溶液的制备方法，如图1所示，该制备方法包括如下步骤：
S01：提供初始氧化锌纳米颗粒溶液；
S02：向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液。
本申请实施例提供的氧化锌纳米颗粒溶液的制备方法，将醋酸金属盐溶液加入初始氧化锌纳米颗粒溶液中混合，这样溶液中的醋酸金属盐将对初始氧化锌纳米颗粒进行修饰，具体的，醋酸金属盐溶解后羧基会取代初始氧化锌纳米颗粒表面的部分羟基，从而钝化氧化锌纳米颗粒表面缺陷，而羧基与氧化锌纳米颗粒的结合力较强，且具有更高的溶解性，由此得到的氧化锌纳米颗粒溶液在存放过程中的不易团聚，稳定性好。
将本申请实施例制备的氧化锌纳米颗粒溶液制备成氧化锌薄膜，用作发光器件的电子传输层时，如量子点发光二极管器件，能够提高发光器件的稳定性，从而提高发光器件的发光效率和使用寿命。
上述步骤S01中，提供的初始氧化锌纳米颗粒溶液是含初始氧化锌纳米颗粒的溶液，既可以是直接购于市场上的初始氧化锌纳米颗粒溶于溶剂后得到的溶液，也可以上直接用锌盐为原料进行溶胶凝胶反应得到的初始氧化锌纳米颗粒溶液。初始氧化锌纳米颗粒溶液中的溶剂可以是醇溶剂，如甲醇、乙醇、丙醇等，醇溶剂可以用于分散氧化锌纳米颗粒。
在一个实施例中，初始氧化锌纳米颗粒溶液中的初始氧化锌纳米颗粒浓度为10~60mg/mL，例如10mg/mL、15mg/mL、20mg/mL、30mg/mL、40mg/mL、50mg/mL、60mg/mL等。上述浓度范围内，初始氧化锌纳米颗粒分散均匀，可以和醋酸盐溶液充分反应。
上述S02中，向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液混合，这样溶液中的醋酸金属盐将对初始氧化锌纳米颗粒进行修饰。提供的醋酸金属盐溶液中，醋酸金属盐浓度可以是10~30mg/mL，例如10mg/mL、15mg/mL、20mg/mL、25mg/mL、30mg/mL等，上述浓度范围内，醋酸金属盐溶液中的醋酸金属盐分散均匀。
在一个实施例中，初始氧化锌纳米颗粒溶液中的锌离子与醋酸金属盐溶液中的醋酸金属盐的摩尔比为（2~10）：1，例如2：1、4：1、5：1、6：1、8：1、10：1等。在上述摩尔比范围内，醋酸金属盐既可以很好地修饰氧化锌纳米颗粒，又不会过度消耗材料。
在一个实施例中，醋酸金属盐溶液中的醋酸金属盐包括但不限于醋酸镁、醋酸铝、醋酸钠、醋酸钾和醋酸锌中的至少一种，例如可以是上述醋酸金属盐中的一种，也可以是上述醋酸金属盐中两种或多种的组合。上述醋酸金属盐中的金属离子不为锌离子（例如，是镁离子、铝离子、钾离子或钠离子），这样可以对初始氧化锌纳米颗粒表面的部分锌离子进行置换，从而可以对氧化锌的电子结构进行一定程度的调节，优化氧化锌的电学性能。由此得到的氧化锌纳米颗粒溶液，不仅存放过程中不易团聚，稳定性好，而且氧化锌纳米颗粒电学性能也得到提高。
在一个实施例中，氧化锌纳米颗粒溶液的制备方法还包括：向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液后，采用乙醇和/或乙酸乙酯清洗加入了醋酸金属盐溶液后的初始氧化锌纳米颗粒溶液，并将清洗后的氧化锌纳米颗粒溶于醇溶剂，得到氧化锌纳米颗粒溶液。醋酸金属盐中的羧基可以很好地钝化氧化锌纳米颗粒表面缺陷，提高氧化锌纳米颗粒稳定性，使氧化锌纳米颗粒溶液在存放过程中不易团聚，再经过上述清洗步骤，得到纯化的氧化锌纳米颗粒溶液用于成膜，可以得到稳定性好的氧化锌薄膜，用作量子点发光二极管的电子传输层也提高了氧化锌在器件中的稳定性。
在一个实施例中，醋酸金属盐溶液中的溶剂为醇溶剂，与初始氧化锌纳米颗粒溶液的溶剂是相同或不同的醇溶剂，在醇溶剂体系下混合，稳定性好，不影响醋酸金属盐对初始氧化锌纳米颗粒的修饰。
上述醇溶剂选自甲醇、乙醇和丙醇中的至少一种。醋酸金属盐溶液中的醇溶剂、初始氧化锌纳米颗粒溶液中的醇溶剂和清洗后的氧化锌纳米颗粒所溶的醇溶剂可选自相同的单组分醇溶剂，或不同的单组分醇溶剂，或其中两种选自同一种单组份醇溶剂，另一种为不同的单组分醇溶剂，还可以为任意相同或不同的醇溶剂组合。醇溶剂不仅可以很好地分散氧化锌纳米颗粒，而且可以溶解醋酸金属盐，在醇溶剂体系中，醋酸金属盐可以对初始氧化锌纳米颗粒表面进行充分修饰，最终得到稳定的氧化锌纳米颗粒溶液。
本申请一些实施例提供一种氧化锌薄膜的制备方法，如图2所示，该制备方法包括如下步骤：
E01：提供初始氧化锌纳米颗粒溶液，向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
E02：将氧化锌纳米颗粒溶液旋涂在基板上，随后进行加热处理，得到氧化锌薄膜。
本申请实施例提供的氧化锌薄膜的制备方法，采用本申请上述特有的氧化锌纳米颗粒溶液的制备方法得到的氧化锌纳米颗粒溶液进行旋涂，因该用于成膜的氧化锌纳米颗粒溶液中加入有醋酸金属盐溶液，从而可以制备得到稳定性好的氧化锌薄膜，该稳定的氧化锌薄膜可以用作量子点发光二极管的电子传输层，能够提高器件的稳定性，具有很好的前景。
上述步骤E01，即为氧化锌纳米颗粒溶液的制备过程。本申请实施例用于成膜的氧化锌纳米颗粒溶液是前述氧化锌纳米颗粒溶液的制备方法得到的氧化锌纳米颗粒溶液，前述提到的初始氧化锌纳米颗粒溶液的浓度和溶剂种类，醋酸金属盐溶液的浓度、醋酸金属盐种类和溶剂种类，以及相关的摩尔比例和清洗步骤等可选方案均可以用于步骤E01中。因此，上述步骤E01制备的氧化锌纳米颗粒溶液具有上述实施例氧化锌纳米颗粒溶液的制备方法提供的可选方案的所有优势，在此不再赘述。
上述步骤E02，为氧化锌纳米颗粒溶液成膜过程，其中加热处理的温度可以为60~100℃，如600℃、70℃、90℃、100℃等，加热处理的时间可以为10~30min，如10min、15min、20min、25min等。上述条件下可以更好地使溶剂蒸发，形成稳定的氧化锌薄膜。
本申请一些实施例还提供一种量子点发光二极管的制备方法，如图3所示，该制备方法包括如下步骤：
T01：提供基板；
T02：提供初始氧化锌纳米颗粒溶液，向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
T03：将氧化锌纳米颗粒溶液旋涂在基板上，随后进行加热处理，得到电子传输层。
氧化锌的稳定性对器件性能会有很大影响，分为氧化锌溶液的存放稳定性和氧化锌对器件稳定性的影响。本申请实施例中，用醋酸金属盐对初始氧化锌纳米颗粒溶液进行改性，羧基会取代氧化锌纳米颗粒表面部分羟基，羧基与氧化锌纳米颗粒的结合力较强，且具有更高的溶解性，从而提高氧化锌纳米颗粒溶液的存放稳定性；此外羧基较羟基的稳定性高，可以更好地钝化氧化锌表面缺陷，消除氧化锌缺陷能级，减少量子点发光层与电子传输层界面处的荧光淬灭，提高器件发光效率。因此，通过该制备方法最终提高了制得的量子点发光二极管器件的发光效率和使用寿命。
在一个实施例中，醋酸金属盐溶液中的醋酸金属盐可以选自醋酸镁、醋酸铝、醋酸钠、醋酸钾和醋酸锌中的至少一种，例如，醋酸金属盐采用醋酸镁，也可以同时采用醋酸钠和醋酸锌，或者同时采用醋酸铝、醋酸钠和醋酸钾，这样，向初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液后，醋酸金属盐中的金属离子如钠离子、钾离子、铝离子或镁离子可以置换出氧化锌表面部分的锌离子，对氧化锌纳米颗粒的电子结构进行一定程度的调节，优化氧化锌的电学性能，从而可以提高量子点发光二极管的发光性能。
上述步骤T01，根据量子点发光二极管的正置或倒置类型，提供的基板可以是表面沉积有各种功能层的基板。
在一个实施例中，该量子点发光二极管为正置型器件，其制备方法可以包括如下步骤：提供基板，基板表面制备有阳极，阳极上制备有量子点发光层；采用本申请前述氧化锌薄膜的制备方法在基板上的量子点发光层表面制备氧化锌薄膜，得到电子传输层；然后在电子传输层上制备阴极。具体地，在阳极上制备量子点发光层之前，可以先在阳极上制备空穴功能层（如制备空穴传输层，或者依次制备层叠的空穴注入层和空穴传输层），再于该空穴功能层上制备该量子点发光层。具体地，在电子传输层上制备阴极之前，可以先在电子传输层上制备电子注入层，然后在电子注入层上制备该阳极。
在一个实施例中，该量子点发光二极管为倒置型器件，其制备方法可以包括如下步骤：提供基板，基板上制备有阴极；采用本申请前述氧化锌薄膜的制备方法在基板上的阴极表面制备氧化锌薄膜，得到电子传输层；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阳极。具体地，在量子点发光层上制备阳极之前，可以先在量子点发光层上制备空穴功能层（如制备空穴传输层，或者依次制备层叠的空穴传输层和空穴注入层），再于该空穴功能层上制备该阳极。具体地，在基板的阴极上制备该电子传输层之前，可以先在阴极上制备电子注入层，然后在电子注入层上制备该电子传输层。
上述步骤T02，即为用于制备电子传输层的氧化锌纳米颗粒溶液的配制过程。本申请实施例用于制成电子传输层的氧化锌纳米颗粒溶液是前述氧化锌纳米颗粒溶液的制备方法得到的氧化锌纳米颗粒溶液，前述提到的初始氧化锌纳米颗粒溶液的浓度和溶剂种类，醋酸金属盐溶液的浓度、醋酸金属盐种类和溶剂种类，以及相关的摩尔比例和清洗步骤等可选方案均可以用于步骤T02中。因此，上述步骤T02制备的氧化锌纳米颗粒溶液具有上述实施例氧化锌纳米颗粒溶液的制备方法提供的可选方案的所有优势，在此不再赘述。
上述步骤T03，为氧化锌纳米颗粒溶液成膜形成电子传输层的过程，其中加热处理的温度可以为60~100℃，如600℃、70℃、90℃、100℃等，加热处理的时间可以为10~30min，如10min、15min、20min、25min等。上述条件下可以更好地使溶剂蒸发，形成稳定的电子传输层。
本申请实施例还提供一种量子点发光二极管，该量子点发光二极管由上述量子点发光二极管的制备方法制备得到。该器件具有良好的发光效率和使用寿命。
具体地，该量子点发光二极管包括阳极、阴极以及设置在阳极和阴极之间的量子点发光层，阴极与量子点发光层之间设置有电子传输层，该电子传输层即为本申请实施例提供的氧化锌薄膜的制备方法得到的氧化锌薄膜。
在一个实施例中，量子点发光二极管的电子传输层与阴极之间还可以设置电子注入层。或者，阳极与量子点发光层之间还可以设置空穴传输层。此外，阳极与空穴传输层之间还可以设置空穴注入层。
下面结合具体实施例进行说明。
实施例1
氧化锌纳米颗粒溶液的制备，包括如下步骤
（1）向10mL初始氧化锌纳米颗粒乙醇溶液（氧化锌的质量浓度为40mg/mL）中，加入5mL的醋酸镁乙醇溶液（醋酸镁的质量浓度为20mg/mL），搅拌10min得到混合溶液；
（2）向上述混合溶液中加入乙酸乙酯进行沉淀清洗，离心分离后将沉淀物重新溶于乙醇中，再重复一次该步骤，得到修饰后的氧化锌纳米颗粒溶液。
实施例2
氧化锌薄膜的制备，包括如下步骤：
（1）将实施例1制备得到的氧化锌纳米颗粒溶液（氧化锌的质量浓度浓度为30mg/mL）旋涂在基板上；其中，旋涂转速为3000转每分钟，旋涂时间30s；
（2）旋涂结束后在80℃下加热20min，得到氧化锌薄膜。
实施例3
量子点发光二极管的制备，包括如下步骤：
（1）在基板上蒸镀ITO做阳极，ITO的厚度为40nm，之后UVO（紫外光臭氧）清洗15min，清洗表面的同时改善表面浸润度，并提高ITO的功函数。
（2）在阳极上旋涂一层PEDOT:PSS做空穴注入层，旋涂转速为4000转每分钟，旋涂40s，之后在150℃退火15min，整个步骤在空气中进行。
（3）在空穴注入层上旋涂一层TFB做空穴传输层；具体是将TFB溶解在氯苯中，形成浓度为8mg/mL的溶液，然后以转速为3000转每分钟进行旋涂，旋涂时间30s，之后在150℃下退火20min，整个步骤在手套箱中进行。
（4）在空穴传输层上旋涂量子点发光层；具体是将量子点溶解在正辛烷中，形成浓度为20mg/mL的量子点溶液，然后以转速为3000转每分钟进行旋涂，旋涂30s，之后在100℃下加热20min，该步骤在手套箱中进行。
（5）在量子点发光层上旋涂电子传输层：
将实施例1制备得到的氧化锌纳米颗粒溶液（氧化锌的质量浓度浓度为30mg/mL）直接以转速为3000转每分钟进行旋涂，旋涂时间30s，之后在80℃下加热20min，该步骤在手套箱中进行。
（6）在电子传输层上蒸镀100nm的Al做阴极。
实施例4
量子点发光二极管的制备，包括如下步骤：
（1）在基板上蒸镀ITO做阳极，ITO的厚度为40nm，之后UVO（紫外光臭氧）清洗15min，清洗表面的同时改善表面浸润度，并提高ITO的功函数。
（2）在阳极上旋涂一层PEDOT:PSS做空穴注入层，旋涂转速为4000转每分钟，旋涂40s，之后在150℃退火15min，整个步骤在空气中进行。
（3）在空穴注入层上旋涂一层TFB做空穴传输层；具体是将TFB溶解在氯苯中，形成浓度为8mg/mL的溶液，然后以转速为3000转每分钟进行旋涂，旋涂时间30s，之后在150℃下退火20min，整个步骤在手套箱中进行。
（4）在空穴传输层上旋涂量子点发光层；具体是将量子点溶解在正辛烷中，形成浓度为20mg/mL的量子点溶液，然后以转速为3000转每分钟进行旋涂，旋涂30s，之后在100℃下加热20min，该步骤在手套箱中进行。
（5）在量子点发光层上旋涂电子传输层：
将实施例1制备得到的氧化锌纳米颗粒溶液（氧化锌的质量浓度浓度为30mg/mL）在5℃的冰箱中存放14天后，以转速为3000转每分钟进行旋涂，旋涂时间30s，之后在80℃下加热20min，该步骤在手套箱中进行。
（6）在电子传输层上蒸镀100nm的Al做阳极。
实施例5
一种量子点发光二极管，如图4所示，从下到上依次：基板10，阳极1，空穴注入层2，空穴传输层3，量子点发光层4，电子传输层5，阴极6。
该器件使用实施例3的步骤制备得到。
实施例6
一种量子点发光二极管，如图4所示，从下到上依次：基板10，阳极1，空穴注入层2，空穴传输层3，量子点发光层4，电子传输层5，阴极6。
该器件使用实施例4的步骤制备得到。
对比例
一种量子点发光二极管，如图4所示，从下到上依次：基板10，阳极1，空穴注入层2，空穴传输层3，量子点发光层4，电子传输层5，阴极6。
该器件的制备步骤中，除了电子传输层的制备使用实施例1中未修饰的初始氧化锌纳米颗粒乙醇溶液（配制的氧化锌质量浓度为30mg/mL）外，其他步骤均与实施例3相同。
性能测试
（1）将实施例1制备的氧化锌纳米颗粒溶液进行颗粒粒径测试，具体测试方法为：将氧化锌纳米颗粒溶液通过散射法用激光粒径分布测试仪测试得到颗粒粒径，结果如表1所示：
表1
实施例1制备的氧化锌纳米颗粒溶液 氧化锌纳米颗粒颗径
制备步骤刚结束 5.0nm
制备步骤结束后置于5℃冰箱中存放14天 5.1nm
（2）将实施例5-6和对比例的器件进外量子效率和寿命性能测试，具体测试方法为：器件外量子效率通过JVL效率测试设备测试获得，器件寿命通过寿命测试设备在大电流下加速测试然后换算得到，结果如表2所示：
表2
项目组别 外量子效率（EQE） T95(1000nit)
实施例5 19.5% 7410h
实施例6 20.1% 6300h
对比例 17.1% 2100h
注：T95(1000nit)指亮度从1000nit衰减至95%所需要的时间。
从表1和表2的数据可知，本申请实施例的氧化锌纳米颗粒溶液的制备方法可以明显提高氧化锌纳米颗粒溶液的存放稳定性，将此类氧化锌纳米颗粒溶液用于制备量子点发光二极管的电子传输层，可以提高器件的发光效率和使用寿命。
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。

Claims (20)

  1. 一种氧化锌纳米颗粒溶液的制备方法，其中，包括如下步骤：
    提供初始氧化锌纳米颗粒溶液；
    向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到所述氧化锌纳米颗粒溶液。
  2. 根据权利要求1所述的氧化锌纳米颗粒溶液的制备方法，其中，所述初始氧化锌纳米颗粒溶液的浓度为10~60mg/mL；
    和/或所述初始氧化锌纳米颗粒溶液中的锌离子与所述醋酸金属盐溶液中的醋酸金属盐的摩尔比为（2~10）：1。
  3. 如权利要求1所述的氧化锌纳米颗粒溶液的制备方法，其中，所述醋酸金属盐溶液中的醋酸金属盐选自醋酸镁、醋酸铝、醋酸钠和醋酸钾中的至少一种。
  4. 如权利要求1所述的氧化锌纳米颗粒溶液的制备方法，其中，所述初始氧化锌纳米颗粒溶液的溶剂与所述醋酸金属盐溶液的溶剂是相同或不同的醇溶剂。
  5. 如权利要求4所述的氧化锌纳米颗粒溶液的制备方法，其中，所述醇溶剂选自甲醇、乙醇和丙醇中的至少一种。
  6. 如权利要求1所述的氧化锌纳米颗粒溶液的制备方法，其中，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液后，还包括：采用乙醇和/或乙酸乙酯清洗加入了所述醋酸金属盐溶液后的初始氧化锌纳米颗粒溶液，并将清洗后的氧化锌纳米颗粒溶于醇溶剂，得到所述氧化锌纳米颗粒溶液。
  7. 一种氧化锌薄膜的制备方法，其中，包括如下步骤：
    提供初始氧化锌纳米颗粒溶液，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
    将所述氧化锌纳米颗粒溶液旋涂在基板上，随后进行加热处理，得到所述氧化锌薄膜。
  8. 根据权利要求7所述的氧化锌薄膜的制备方法，其中，所述初始氧化锌纳米颗粒溶液的浓度为10~60mg/mL；
    和/或所述初始氧化锌纳米颗粒溶液中的锌离子与所述醋酸金属盐溶液中的醋酸金属盐的摩尔比为（2~10）：1。
  9. 如权利要求7所述的氧化锌薄膜的制备方法，其中，所述醋酸金属盐溶液中的醋酸金属盐选自醋酸镁、醋酸铝、醋酸钠和醋酸钾中的至少一种。
  10. 如权利要求7所述的氧化锌薄膜的制备方法，其中，所述初始氧化锌纳米颗粒溶液的溶剂与所述醋酸金属盐溶液的溶剂是相同的醇溶剂。
  11. 如权利要求10所述的氧化锌薄膜的制备方法，其中，所述醇溶剂选自甲醇、乙醇和丙醇中的至少一种。
  12. 如权利要求7所述的氧化锌薄膜的制备方法，其中，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液后，还包括：采用乙醇和乙酸乙酯中的至少一种清洗加入了所述醋酸金属盐溶液后的初始氧化锌纳米颗粒溶液，并将清洗后的氧化锌纳米颗粒溶于醇溶剂，得到所述氧化锌纳米颗粒溶液。
  13. 如权利要求7所述的氧化锌薄膜的制备方法，其中，所述加热处理的温度为60~100℃，所述加热处理的时间为10~30min。
  14. 一种量子点发光二极管的制备方法，其中，包括如下步骤：
    提供基板；
    提供初始氧化锌纳米颗粒溶液，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液，得到氧化锌纳米颗粒溶液；
    将所述氧化锌纳米颗粒溶液旋涂在所述基板上，随后进行加热处理，得到电子传输层。
  15. 根据权利要求14所述的量子点发光二极管的制备方法，其中，所述初始氧化锌纳米颗粒溶液的浓度为10~60mg/mL；
    和/或所述初始氧化锌纳米颗粒溶液中的锌离子与所述醋酸金属盐溶液中的醋酸金属盐的摩尔比为（2~10）：1。
  16. 如权利要求14所述的量子点发光二极管的制备方法，其中，所述醋酸金属盐溶液中的醋酸金属盐选自醋酸镁、醋酸铝、醋酸钠和醋酸钾中的至少一种。
  17. 如权利要求14所述的量子点发光二极管的制备方法，其中，所述初始氧化锌纳米颗粒溶液的溶剂与所述醋酸金属盐溶液的溶剂是相同的醇溶剂。
  18. 如权利要求17所述的量子点发光二极管的制备方法，其中，所述醇溶剂选自甲醇、乙醇和丙醇中的至少一种。
  19. 如权利要求14所述的量子点发光二极管的制备方法，其中，向所述初始氧化锌纳米颗粒溶液中加入醋酸金属盐溶液后，还包括：采用乙醇和乙酸乙酯中的至少一种清洗加入了所述醋酸金属盐溶液后的初始氧化锌纳米颗粒溶液，并将清洗后的氧化锌纳米颗粒溶于醇溶剂，得到所述氧化锌纳米颗粒溶液。
  20. 如权利要求14所述的量子点发光二极管的制备方法，其中，所述加热处理的温度为60~100℃，所述加热处理的时间为10~30min。
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