WO2020134252A1 - Composite material, thin film and preparing method therefor and quantum dot light-emitting diode - Google Patents

Composite material, thin film and preparing method therefor and quantum dot light-emitting diode Download PDF

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WO2020134252A1
WO2020134252A1 PCT/CN2019/108154 CN2019108154W WO2020134252A1 WO 2020134252 A1 WO2020134252 A1 WO 2020134252A1 CN 2019108154 W CN2019108154 W CN 2019108154W WO 2020134252 A1 WO2020134252 A1 WO 2020134252A1
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graphene
mixed solution
substrate
quantum dot
composite material
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PCT/CN2019/108154
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French (fr)
Chinese (zh)
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张涛
向超宇
朱佩
罗植天
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Tcl科技集团股份有限公司
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Publication of WO2020134252A1 publication Critical patent/WO2020134252A1/en

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    • 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
    • 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
    • H10K50/165—Electron transporting layers comprising dopants
    • 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

Definitions

  • the present application belongs to the field of display technology, and particularly relates to a composite material, a film and a preparation method thereof, and a quantum dot light-emitting diode.
  • a method for manufacturing a quantum dot light-emitting diode including the following steps:
  • nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
  • a first substrate is provided, the mixed solution is deposited on the surface of the first substrate, dried to form a film, and an electron transport layer is prepared.
  • the composite material provided in this application uses nano-zinc oxide as the main body of the material, and at the same time, graphene material is compounded.
  • the work function (-4.42eV) is lower than the nano-zinc oxide conduction band (-4.05eV).
  • the composite material of nano-zinc oxide and an appropriate amount of graphene is used as the material of the electron transport layer of the quantum dot light-emitting device, the electron can be further transferred to the valence band of the quantum dot, the probability of exciton quenching can be reduced, and the luminous efficiency of the device can be improved.
  • the amount of graphene added in the composite material is not as large as possible.
  • the weight percentage of the graphene is 0.1% to 10%, and the resulting composite material can be effective when used as an electron transport material for a light emitting diode It avoids the further transmission of electrons to the valence band of quantum dots, reduces the chance of exciton quenching, and improves the luminous efficiency of the device.
  • the graphene content is excessive, the excessive graphene incorporated into the nano-zinc oxide will significantly reduce the nano-zinc oxide's Fermi energy level, promote the transfer of electrons at the interface from the nano-zinc oxide to the quantum dot light-emitting layer, and destroy the quantum dot light emission
  • the charge balance in the diode reduces the luminous efficiency of the device.
  • the thin film and thin film material provided by the present application are composite materials of the above nano zinc oxide and graphene. Therefore, when the thin film is used as an electron transport layer of a light-emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the preparation method of the thin film provided by the present application is to disperse graphene and nano-zinc oxide in an organic solvent according to the amount ratio, and after mixing, disperse it ultrasonically, deposit the obtained mixed solution on the target substrate surface of the thin film to be deposited, and then dry it. get.
  • This method is not only simple and easy to operate, but when the resulting thin film is used as an electron transport layer of a light emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the quantum dot light emitting diode provided by the present application includes an electron transport layer, and the material of the electron transport layer is a composite material of the above-mentioned nano zinc oxide and graphene.
  • the quantum dot light-emitting diode thus obtained can effectively prevent electrons from further transmitting to the valence band of the quantum dot, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the preparation method of the quantum dot light-emitting diode provided by the present application disperses graphene and nano-zinc oxide in an organic solvent according to the amount ratio, mixes and disperses ultrasonically, and deposits the obtained mixed solution on the surface of the first substrate of the thin film to be deposited.
  • the electron transport layer can be obtained by drying. The method is not only simple and easy to operate, but also the obtained electron transport layer can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the
  • An embodiment of the present application provides a composite material, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the weight percentage content of the graphene is 0.1% ⁇ 10%.
  • the composite material provided by the embodiment of the present application uses nano-zinc oxide as the main body of the material, and at the same time, graphene material is compounded.
  • the work function (-4.42eV) is lower than the nano-zinc oxide conduction band (-4.05eV).
  • the electron can be further transferred to the valence band of the quantum dot, the probability of exciton quenching can be reduced, and the luminous efficiency of the device can be improved.
  • the more graphene is added in the composite material the better.
  • the weight percentage of the graphene is 0.1% to 10%, and the resulting composite material can be effective when used as an electron transport material for a light emitting diode It avoids the further transmission of electrons to the valence band of quantum dots, reduces the chance of exciton quenching, and improves the luminous efficiency of the device.
  • the graphene content is excessive, the excessive graphene incorporated into the nano-zinc oxide will significantly reduce the nano-zinc oxide's Fermi energy level, promote the transfer of electrons at the interface from the nano-zinc oxide to the quantum dot light-emitting layer, and destroy the quantum dot light emission
  • the charge balance in the diode reduces the luminous efficiency of the device.
  • the composite material of nano-zinc oxide and an appropriate amount of graphene is used as the electron transport layer material of the quantum dot light-emitting device, the valence band of further electron transmission to the quantum dot can be better avoided, reducing the probability of exciton quenching and improving Device luminous efficiency.
  • An embodiment of the present application provides a film, the material of the film includes a composite material, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the graphene The weight percentage is 0.1% ⁇ 10%.
  • the film material is a composite material of the foregoing nano zinc oxide and graphene. Therefore, when the thin film is used as an electron transport layer of a light-emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the weight percentage of the graphene is 3% to 10%, so that when the thin film is used as an electron transport layer, It can avoid the further transmission of electrons to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the weight percentage of graphene is distributed along a gradient perpendicular to the film.
  • the thin film is used as an electron transport layer of a light emitting device, especially a quantum dot light emitting diode, along the direction of the light emitting layer such as the quantum dot light emitting layer to the cathode, the graphene concentration in the thin film gradually increases to form graphite Graphene/ZnO composite electron transport layer with a gradient distribution of olefins. At this time, the concentration of ZnO at the end near the quantum dot light emitting layer is high.
  • the film provided in the examples of the present application can be prepared by the following method.
  • the embodiment of the present application provides a method for preparing a thin film, including the following steps:
  • nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and subjected to ultrasonic treatment to obtain a mixed solution;
  • the mixed solution is deposited on the surface of the substrate and dried to form a film.
  • graphene and nano-zinc oxide are dispersed in an organic solvent according to the amount ratio, and after mixing, they are ultrasonically dispersed, and the resulting mixed solution is deposited on the target substrate surface of the thin film to be deposited, and dried To get it.
  • This method is not only simple and easy to operate, but when the resulting thin film is used as an electron transport layer of a light emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • both the nano-zinc oxide and the graphene can be prepared by reference to existing methods.
  • the preparation method of zinc oxide is: dissolving zinc acetate in dimethyl sulfoxide, dissolving tetramethyl ammonium hydroxide in ethanol, and then mixing and processing, stirring the reaction at room temperature; adding acetic acid after the reaction Ethyl acetate, remove the supernatant after centrifugation; add ethanolamine and ethanol to stabilize the nanoparticles after collecting the precipitate, then wash with ethyl acetate, centrifuge to remove the supernatant, and dry to obtain ZnO nanoparticles.
  • the method for preparing graphene is: using a hummer method to prepare graphene oxide, and then reducing the graphene oxide with hydrazine hydrate to obtain graphene.
  • an organic solution of graphene and an organic solution of nano-zinc oxide are provided separately. According to a ratio of 0.1% to 10% of the total weight of graphene and nano-zinc oxide, the organic solution and nano-graphene of graphene The organic solution of zinc oxide is mixed.
  • the solvent in the organic solution of graphene can be an organic solvent that can effectively disperse graphene, in some embodiments, organic alcohols; the solvent in the organic solution of nano-zinc oxide can effectively disperse nano-oxide
  • the organic solvents of zinc and graphene are, in some embodiments, organic alcohols.
  • the solvent in the organic solution of graphene and the solvent in the organic solution of nano-zinc oxide are both ethanol.
  • graphene and nano-zinc oxide are provided separately, and the graphene and nano-zinc oxide are dispersed in an organic solvent and subjected to mixing treatment.
  • the organic solvent is an organic solvent that can effectively disperse nano-zinc oxide and graphene at the same time, in some embodiments, organic alcohols, and in some embodiments, ethanol.
  • the nano-zinc oxide and graphene After dispersing the nano-zinc oxide and graphene in an organic solvent, they are mixed and processed. In order to make the two dispersed evenly, the obtained dispersion system was sonicated. In some embodiments, ultrasound is performed in a natural state for 4 to 6 hours to obtain a mixed solution.
  • depositing the mixed solution on the surface of the substrate can be achieved by a conventional solution processing method, such as inkjet printing, spin coating, and the like. Further, the film is formed after drying treatment.
  • the substrate is any substrate that needs to deposit the mixed solution.
  • the substrate may be laminated Anode/quantum dot light emitting layer stack, anode/hole function layer/quantum dot light emitting layer stack, cathode, cathode/electron injection layer stack.
  • the mixed solution is deposited on the surface of the substrate, and the method of drying the film is:
  • the temperature of the bottom plate is 60°C to 80°C
  • the temperature of the top plate is 80°C to 120°C.
  • the temperature difference between the bottom plate and the top plate is greater than or equal to 20°C.
  • a temperature gradient is formed.
  • the zinc oxide nanoparticles supported on the graphene by physical adsorption will form from the top (side close to the top plate) to the bottom (close to the top plate)
  • a composite graphene/ZnO thin film with a low nano zinc oxide concentration on the top and a high nano zinc oxide concentration on the bottom is formed.
  • the mixed solution is deposited on the surface of the substrate, and the method of drying the film is:
  • the mixed solution is deposited on the surface of the substrate, the substrate on which the mixed solution is deposited is placed on a hot plate, and heat treatment is performed under the condition that the hot plate is connected with a positive voltage to prepare a thin film.
  • an embodiment of the present application further provides a quantum dot light-emitting diode, including an anode 1 and a cathode 6 disposed oppositely, a quantum dot light-emitting layer 4 disposed between the anode 1 and the cathode 6, and a cathode disposed 6 and the electron transport layer 5 between the quantum dot light emitting layer 4, wherein the material of the electron transport layer 5 is the composite material described in the embodiments of the present application, or the electron transport layer 5 is the thin film described in the embodiments of the present application.
  • the quantum dot light emitting diode provided by the embodiment of the present application includes an electron transport layer, and the material of the electron transport layer is a composite material of the above-mentioned nano zinc oxide and graphene.
  • the quantum dot light-emitting diode thus obtained can effectively prevent electrons from further transmitting to the valence band of the quantum dot, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the quantum dot light emitting diode further includes at least one of a hole functional layer and a hole injection layer disposed between the anode 1 and the quantum dot light emitting layer 4.
  • the quantum dot light emitting diode includes a hole function layer 2 disposed between the anode 1 and the quantum dot light emitting layer 4.
  • the quantum dot light emitting diode includes a hole injection layer 3 disposed between the anode 1 and the quantum dot light emitting layer 4.
  • the quantum dot light emitting diode includes a hole function layer 2 disposed between the anode 1 and the quantum dot light emitting layer 4, and a space disposed between the hole transport layer 2 and the quantum dot light emitting layer 4 Hole injection layer 3.
  • the quantum dot light emitting diode further includes an electron injection layer (not shown in the figure) disposed between the cathode 6 and the electron transport layer 5.
  • the embodiments of the present application provide a method for manufacturing a quantum dot light emitting diode, including the following steps:
  • nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
  • a first substrate is provided, the mixed solution is deposited on the surface of the first substrate, dried to form a film, and an electron transport layer is prepared.
  • the preparation method of the quantum dot light-emitting diode provided in the embodiment of the present application disperses graphene and nano-zinc oxide in an organic solvent according to the amount ratio, and after mixing, disperses ultrasonically to deposit the resulting mixed solution on the surface of the first substrate of the thin film to be deposited After drying, the electron transport layer can be obtained.
  • the method is not only simple and easy to operate, but also the obtained electron transport layer can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
  • the steps for preparing the electron transport layer on the surface of the first substrate and the preferred situations thereof are as described above. In order to save space, they will not be repeated here.
  • the first substrate includes an anode, and a quantum dot light emitting layer provided on the anode.
  • the first substrate further includes a hole function layer disposed between the anode and the quantum dot light emitting layer.
  • the hole functional layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
  • the anode is an anode disposed on the substrate.
  • the electron transport layer after preparing the electron transport layer, it further includes preparing a cathode on the surface of the electron transport layer facing away from the quantum dot light emitting layer. In some embodiments, before preparing the cathode, it further includes preparing an electron injection layer on the surface of the electron transport layer facing away from the quantum dot light emitting layer.
  • the method further includes preparing a quantum dot light-emitting layer on the surface of the electron transport layer facing away from the cathode, and preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode.
  • the anode before preparing the anode, it further includes preparing a hole function layer on the surface of the quantum dot light-emitting layer facing away from the cathode.
  • the hole functional layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
  • a quantum dot light-emitting diode includes a substrate, an anode and a cathode provided on the substrate, and a laminated structure provided between the anode and the cathode, the laminated structure includes a layered hole injection layer -A hole transport layer-a quantum dot light emitting layer-an electron transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the electron transport layer is disposed adjacent to the cathode.
  • the preparation method of the quantum dot light-emitting diode includes the following steps:
  • the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, and is placed in a heatable device, wherein the heatable device includes a bottom plate and a top plate that are opposite and arranged in parallel, and the mixture is deposited
  • the substrate of the solution is placed in the sealable device parallel to the bottom plate.
  • Heat-treating the sealable device so that the heating temperature of the bottom plate is 60°C and the heating temperature of the top plate is 80°C, and after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed;
  • the cathode is deposited on the electron transport layer, and the device preparation is completed after packaging.
  • Example 1 The difference from Example 1 is that the heating temperature of the bottom plate is 60° C., the heating temperature of the top plate is 100° C., and the height between the bottom plate and the top plate is h.
  • the substrate is placed between h/3 ⁇ 2h/3.
  • Example 1 The difference from Example 1 is that the heating temperature of the bottom plate is 60° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h.
  • the substrate is placed between h/3 ⁇ 2h/3.
  • Example 1 The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 90° C., and the height between the bottom plate and the top plate is calculated as h.
  • the substrate is placed between h/3 ⁇ 2h/3.
  • Example 2 The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 105° C., and the height between the bottom plate and the top plate is h, and the mixed solution deposited The substrate is placed between h/3 ⁇ 2h/3.
  • Example 1 The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h.
  • the substrate is placed between h/3 ⁇ 2h/3.
  • Example 1 The difference from Example 1 is that the heating temperature of the bottom plate is 80° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h.
  • the substrate is placed between h/3 ⁇ 2h/3.
  • a quantum dot light-emitting diode includes a substrate, an anode and a cathode provided on the substrate, and a laminated structure provided between the anode and the cathode, the laminated structure includes a layered hole injection layer -A hole transport layer-a quantum dot light emitting layer-an electron transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the electron transport layer is disposed adjacent to the cathode.
  • the preparation method of the quantum dot light-emitting diode includes the following steps:
  • the graphene/ZnO composite material solution was spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and the positive temperature of the external plate was heated at a temperature of 80° C. After drying, the top ZnO concentration was low after drying 1. Electron transport layer of composite graphene/ZnO with high ZnO concentration at the bottom;
  • Example 2 The difference from Example 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and a positive voltage is connected to the hot plate at a temperature of 120°C Under heating, after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed.

Abstract

A composite material. The composite material is nano-zinc oxide and graphene, and with regard to a total weight of the composite material of 100%, the content of graphene is 0.1%-10% according to weight percentage. When the composite material of nano-zinc oxide and a proper amount of graphene is used as the material for an electron transfer layer of a quantum dot light-emitting device, electrons are avoided to be further transferred to a valence band of quantum dots, thus reducing the possibility of exciton annihilation and improving luminous efficiency of the device.

Description

复合材料、薄膜及其制备方法、量子点发光二极管Composite material, film and preparation method thereof, quantum dot light-emitting diode 技术领域Technical field
本申请属于显示技术领域，尤其涉及一种复合材料，一种薄膜及其制备方法，以及一种量子点发光二极管。The present application belongs to the field of display technology, and particularly relates to a composite material, a film and a preparation method thereof, and a quantum dot light-emitting diode.
背景技术Background technique
量子点发光二极管（QLED）是在阳极和阴极加上直流电压，驱动量子点材料发光的器件，其具有色彩饱和、纯度高、单色性佳、颜色可调以及可用溶液法制备等优点，被认为是下一代平板显示器的优势技术。The quantum dot light-emitting diode (QLED) is a device that applies a DC voltage to the anode and cathode to drive the quantum dot material to emit light. It has the advantages of color saturation, high purity, good monochromaticity, adjustable color, and can be prepared by solution method. It is considered to be the superior technology of the next generation flat panel display.
目前研究较为成熟的QLED通常采用多层结构，器件中包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、阴极。而合格的载流子传输层通常需要有合适的光电性能（包括能带结构、导电性、功函数），良好的稳定性和溶液加工性。ZnO具有宽带隙、高光学透明度、化学和热稳定性好、载流子浓度高、电子传输速率快等特点，是理想的电子传输层材料。然而ZnO中由于存在较多由于氧空位产生的表面缺陷态，会捕获从电极注入的电子，再进一步传输到量子点的价带，淬灭激子，减弱器件发光效率。同时目前主流的QLED器件中（ZnO作为电子传输层，有机物作为空穴传输层），电子传输层电子的传输效率要比空穴传输层空穴的传输效率高很多，因此，为了实现电荷平衡，有研究人员通过在ZnO和量子点发光层（QDs）中间加入阻挡层的方式来减少电子的注入，提高器件发光效率。At present, the more mature QLED usually adopts a multi-layer structure, and the device includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. The qualified carrier transport layer usually needs to have suitable photoelectric properties (including energy band structure, conductivity, work function), good stability and solution processability. ZnO has the characteristics of wide band gap, high optical transparency, good chemical and thermal stability, high carrier concentration, fast electron transfer rate, etc. It is an ideal material for electron transport layer. However, due to the existence of more surface defect states due to oxygen vacancies in ZnO, the electrons injected from the electrode will be captured and then further transmitted to the valence band of the quantum dot, quenching the exciton and weakening the luminous efficiency of the device. At the same time, in the current mainstream QLED devices (ZnO as the electron transport layer and organics as the hole transport layer), the electron transport efficiency of the electron transport layer is much higher than that of the hole transport layer. Therefore, in order to achieve charge balance, Some researchers have reduced the injection of electrons by adding a barrier layer between ZnO and quantum dot light-emitting layers (QDs) to improve the luminous efficiency of the device.
技术问题technical problem
本申请实施例提供了一种一种复合材料、含有上述复合材料的薄膜及其制备方法、含有上述复合材料或薄膜的量子点发光二极管，旨在解决现有技术采用纳米氧化锌作为电子传输层时，表面缺陷态多，淬灭激子，且不利于实现电荷平衡的问题。The embodiments of the present application provide a composite material, a film containing the above composite material and a preparation method thereof, a quantum dot light-emitting diode containing the above composite material or film, aiming to solve the prior art using nano-zinc oxide as the electron transport layer At this time, there are many surface defect states, quenching excitons, and not conducive to the problem of achieving charge balance.
技术解决方案Technical solution
本申请实施例是这样实现的，第一方面，提供了一种复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。The embodiments of the present application are implemented in this way. In the first aspect, a composite material is provided, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material being 100%, the graphene The weight percentage content is 0.1%~10%.
第二方面，提供了一种薄膜，所述薄膜的材料包括复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。In a second aspect, a film is provided, the material of the film includes a composite material, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the graphene The weight percentage is 0.1%~10%.
第三方面，提供了一种薄膜的制备方法，包括以下步骤：In a third aspect, a method for preparing a thin film is provided, including the following steps:
按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；According to the ratio of graphene to the total weight of graphene and nano-zinc oxide 0.1%~10%, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
将所述混合溶液沉积在基底表面，干燥成膜。The mixed solution is deposited on the surface of the substrate and dried to form a film.
第四方面，提供了一种量子点发光二极管，包括相对设置的阳极和阴极，设置在所述阳极和所述阴极之间的量子点发光层，以及设置在所述阴极和所述量子点发光层之间的电子传输层，其中，所述电子传输层的材料为本申请所述的复合材料，或所述电子传输层为本申请所述的薄膜。According to a fourth aspect, there is provided a quantum dot light emitting diode, including an anode and a cathode disposed oppositely, a quantum dot light emitting layer disposed between the anode and the cathode, and a light emitting layer disposed between the cathode and the quantum dot An electron transport layer between layers, wherein the material of the electron transport layer is the composite material described in this application, or the electron transport layer is the film described in this application.
第五方面，提供了一种量子点发光二极管的制备方法，包括以下步骤：According to a fifth aspect, a method for manufacturing a quantum dot light-emitting diode is provided, including the following steps:
按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；According to the ratio of graphene to the total weight of graphene and nano-zinc oxide 0.1%~10%, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
提供第一基板，将所述混合溶液沉积在所述第一基板表面，干燥成膜，制备电子传输层。A first substrate is provided, the mixed solution is deposited on the surface of the first substrate, dried to form a film, and an electron transport layer is prepared.
有益效果Beneficial effect
本申请提供的复合材料，以纳米氧化锌作为材料主体，同时复合有石墨烯材料。所述复合材料中，由于石墨烯是很好的电子受体，功函数（-4.42eV）比纳米氧化锌导带（-4.05eV）低。将适量的石墨烯掺入到纳米氧化锌后，纳米氧化锌表面缺陷态捕获的电子易于迁移到石墨烯中。因此，将纳米氧化锌和适量的石墨烯的复合材料用作量子点发光器件的电子传输层材料时，可以避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。本申请中，所述复合材料中石墨烯的添加量并非越多越好。具体的，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%，由此得到的复合材料用作发光二极管的电子传输材料时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。当石墨烯含量过量时，掺入到纳米氧化锌中的过量石墨烯会显著降低纳米氧化锌的费米能级，促进界面处的电子从纳米氧化锌到量子点发光层传输，破坏量子点发光二极管中的电荷平衡，降低器件发光效率。The composite material provided in this application uses nano-zinc oxide as the main body of the material, and at the same time, graphene material is compounded. In the composite material, since graphene is a good electron acceptor, the work function (-4.42eV) is lower than the nano-zinc oxide conduction band (-4.05eV). After the proper amount of graphene is incorporated into the nano-zinc oxide, electrons trapped in the defect state on the surface of the nano-zinc oxide easily migrate into the graphene. Therefore, when the composite material of nano-zinc oxide and an appropriate amount of graphene is used as the material of the electron transport layer of the quantum dot light-emitting device, the electron can be further transferred to the valence band of the quantum dot, the probability of exciton quenching can be reduced, and the luminous efficiency of the device can be improved. . In this application, the amount of graphene added in the composite material is not as large as possible. Specifically, based on the total weight of the composite material being 100%, the weight percentage of the graphene is 0.1% to 10%, and the resulting composite material can be effective when used as an electron transport material for a light emitting diode It avoids the further transmission of electrons to the valence band of quantum dots, reduces the chance of exciton quenching, and improves the luminous efficiency of the device. When the graphene content is excessive, the excessive graphene incorporated into the nano-zinc oxide will significantly reduce the nano-zinc oxide's Fermi energy level, promote the transfer of electrons at the interface from the nano-zinc oxide to the quantum dot light-emitting layer, and destroy the quantum dot light emission The charge balance in the diode reduces the luminous efficiency of the device.
本申请提供的薄膜，薄膜材料为上述纳米氧化锌和石墨烯的复合材料。因此，将所述薄膜用作发光二极管的电子传输层时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。The thin film and thin film material provided by the present application are composite materials of the above nano zinc oxide and graphene. Therefore, when the thin film is used as an electron transport layer of a light-emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
本申请提供的薄膜的制备方法，将石墨烯和纳米氧化锌按照用量比分散在有机溶剂中，混合后超声分散，将得到的混合溶液沉积在待沉积薄膜的目标基底表面，经干燥处理即可得到。该方法不仅方法简单，易于操作，而且得到的薄膜用作发光二极管的电子传输层时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。The preparation method of the thin film provided by the present application is to disperse graphene and nano-zinc oxide in an organic solvent according to the amount ratio, and after mixing, disperse it ultrasonically, deposit the obtained mixed solution on the target substrate surface of the thin film to be deposited, and then dry it. get. This method is not only simple and easy to operate, but when the resulting thin film is used as an electron transport layer of a light emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
本申请提供的量子点发光二极管，包括电子传输层，所述电子传输层的材料为上述纳米氧化锌和石墨烯的复合材料。由此得到的量子点发光二极管，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。本申请提供的量子点发光二极管的制备方法，将石墨烯和纳米氧化锌按照用量比分散在有机溶剂中，混合后超声分散，将得到的混合溶液沉积在待沉积薄膜的第一基底表面，经干燥处理即可得到电子传输层。该方法不仅方法简单，易于操作，而且得到的电子传输层可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。The quantum dot light emitting diode provided by the present application includes an electron transport layer, and the material of the electron transport layer is a composite material of the above-mentioned nano zinc oxide and graphene. The quantum dot light-emitting diode thus obtained can effectively prevent electrons from further transmitting to the valence band of the quantum dot, reduce the probability of exciton quenching, and improve the luminous efficiency of the device. The preparation method of the quantum dot light-emitting diode provided by the present application disperses graphene and nano-zinc oxide in an organic solvent according to the amount ratio, mixes and disperses ultrasonically, and deposits the obtained mixed solution on the surface of the first substrate of the thin film to be deposited. The electron transport layer can be obtained by drying. The method is not only simple and easy to operate, but also the obtained electron transport layer can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
附图说明BRIEF DESCRIPTION
图1是本申请实施例提供的量子点发光二极管的结构示意图；1 is a schematic structural diagram of a quantum dot light emitting diode provided by an embodiment of the present application;
图2是本申请实施例提供的薄膜的制备方法流程示意图。2 is a schematic flow chart of a method for preparing a film provided by an embodiment of the present application.
本发明的实施方式Embodiments of the invention
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仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solutions and advantages of the present application more clear, the following describes the present application in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.
在本申请的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In the description of the present application, it should be understood that the terms “first” and “second” are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise specifically limited.
本申请实施例提供了一种复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。An embodiment of the present application provides a composite material, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the weight percentage content of the graphene is 0.1%~ 10%.
本申请实施例提供的复合材料，以纳米氧化锌作为材料主体，同时复合有石墨烯材料。所述复合材料中，由于石墨烯是很好的电子受体，功函数（-4.42eV）比纳米氧化锌导带（-4.05eV）低。将适量的石墨烯掺入到纳米氧化锌后，纳米氧化锌表面缺陷态捕获的电子易于迁移到石墨烯中。因此，将纳米氧化锌和适量的石墨烯的复合材料用作量子点发光器件的电子传输层材料时，可以避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。本申请实施例中，所述复合材料中石墨烯的添加量并非越多越好。具体的，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%，由此得到的复合材料用作发光二极管的电子传输材料时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。当石墨烯含量过量时，掺入到纳米氧化锌中的过量石墨烯会显著降低纳米氧化锌的费米能级，促进界面处的电子从纳米氧化锌到量子点发光层传输，破坏量子点发光二极管中的电荷平衡，降低器件发光效率。The composite material provided by the embodiment of the present application uses nano-zinc oxide as the main body of the material, and at the same time, graphene material is compounded. In the composite material, since graphene is a good electron acceptor, the work function (-4.42eV) is lower than the nano-zinc oxide conduction band (-4.05eV). After the proper amount of graphene is incorporated into the nano-zinc oxide, electrons trapped in the defect state on the surface of the nano-zinc oxide easily migrate into the graphene. Therefore, when the composite material of nano-zinc oxide and an appropriate amount of graphene is used as the material of the electron transport layer of the quantum dot light-emitting device, the electron can be further transferred to the valence band of the quantum dot, the probability of exciton quenching can be reduced, and the luminous efficiency of the device can be improved. . In the examples of the present application, the more graphene is added in the composite material, the better. Specifically, based on the total weight of the composite material being 100%, the weight percentage of the graphene is 0.1% to 10%, and the resulting composite material can be effective when used as an electron transport material for a light emitting diode It avoids the further transmission of electrons to the valence band of quantum dots, reduces the chance of exciton quenching, and improves the luminous efficiency of the device. When the graphene content is excessive, the excessive graphene incorporated into the nano-zinc oxide will significantly reduce the nano-zinc oxide's Fermi energy level, promote the transfer of electrons at the interface from the nano-zinc oxide to the quantum dot light-emitting layer, and destroy the quantum dot light emission The charge balance in the diode reduces the luminous efficiency of the device.
本申请实施例中，所述纳米氧化锌和所述石墨烯均为常规的纳米氧化锌和石墨烯，本申请没有严格限定。在一些实施例中，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为3%~10%。此时，所述石墨烯在所述纳米氧化锌中的掺杂量更为合适，能够更好地将纳米氧化锌表面缺陷态捕获的电子迁移到石墨烯中。进而，将纳米氧化锌和适量的石墨烯的复合材料用作量子点发光器件的电子传输层材料时，可以更好地避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。In the examples of this application, the nano-zinc oxide and the graphene are both conventional nano-zinc oxide and graphene, and this application is not strictly limited. In some embodiments, based on the total weight of the composite material being 100%, the weight percentage content of the graphene is 3%-10%. At this time, the doping amount of the graphene in the nano-zinc oxide is more appropriate, and the electrons trapped in the defect state of the nano-zinc oxide surface can be better migrated into the graphene. Furthermore, when the composite material of nano-zinc oxide and an appropriate amount of graphene is used as the electron transport layer material of the quantum dot light-emitting device, the valence band of further electron transmission to the quantum dot can be better avoided, reducing the probability of exciton quenching and improving Device luminous efficiency.
本申请实施例提供了一种薄膜，所述薄膜的材料包括复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。An embodiment of the present application provides a film, the material of the film includes a composite material, the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the graphene The weight percentage is 0.1%~10%.
本申请实施例提供的薄膜，薄膜材料为上述纳米氧化锌和石墨烯的复合材料。因此，将所述薄膜用作发光二极管的电子传输层时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。In the film provided by the embodiment of the present application, the film material is a composite material of the foregoing nano zinc oxide and graphene. Therefore, when the thin film is used as an electron transport layer of a light-emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
在一些实施例中，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为3%~10%，从而，将所述薄膜用作电子传输层时，可以更好地避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。In some embodiments, based on the total weight of the composite material being 100%, the weight percentage of the graphene is 3% to 10%, so that when the thin film is used as an electron transport layer, It can avoid the further transmission of electrons to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
在上述实施例的基础上，在一些实施例中，所述薄膜中，所述石墨烯的重量百分含量沿着垂直于所述薄膜的方向梯度分布。具体的，所述薄膜用作发光器件特别是量子点发光二极管的电子传输层时，沿着发光层如量子点发光层到阴极的方向，所述薄膜中的石墨烯浓度逐渐升高，形成石墨烯梯度分布的石墨烯/ZnO复合电子传输层。此时，靠近量子点发光层的一端ZnO浓度较高，对应地，石墨烯浓度低，薄膜中的石墨烯不容易过量，不至于显著降低ZnO的费米能级，促进界面处的电子从ZnO到量子点发光层传输，破坏QLED器件中的电荷平衡，降低器件发光效率。由此形成的薄膜，能够有效利用石墨烯钝化ZnO，减少ZnO表面缺陷态对激子的淬灭，同时，避免由于过度降低ZnO的费米能级带来的器件电荷不平衡的现象，最终有效提升器件的发光效率。Based on the above embodiments, in some embodiments, in the film, the weight percentage of graphene is distributed along a gradient perpendicular to the film. Specifically, when the thin film is used as an electron transport layer of a light emitting device, especially a quantum dot light emitting diode, along the direction of the light emitting layer such as the quantum dot light emitting layer to the cathode, the graphene concentration in the thin film gradually increases to form graphite Graphene/ZnO composite electron transport layer with a gradient distribution of olefins. At this time, the concentration of ZnO at the end near the quantum dot light emitting layer is high. Correspondingly, the concentration of graphene is low, and the graphene in the film is not easy to be excessive, so that the Fermi level of ZnO is not significantly reduced, and the electrons at the interface are promoted from ZnO. The transmission to the quantum dot light-emitting layer destroys the charge balance in the QLED device and reduces the luminous efficiency of the device. The thin film thus formed can effectively use graphene to passivate ZnO, reduce the quenching of excitons on the surface defect state of ZnO, and at the same time, avoid the device charge imbalance caused by excessively reducing the Fermi level of ZnO. Effectively improve the luminous efficiency of the device.
本申请实施例提供的薄膜，可以通过下述方法制备获得。The film provided in the examples of the present application can be prepared by the following method.
相应的，参照图2示出的本申请实施例的一种薄膜的制备方法的流程示意图，本申请实施例提供了一种薄膜的制备方法，包括以下步骤：Correspondingly, referring to the schematic flow chart of a method for preparing a film according to an embodiment of the present application shown in FIG. 2, the embodiment of the present application provides a method for preparing a thin film, including the following steps:
S01. 按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；S01. According to the ratio of graphene to 0.1% to 10% of the total weight of graphene and nano-zinc oxide, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and subjected to ultrasonic treatment to obtain a mixed solution;
S02. 将所述混合溶液沉积在基底表面，干燥成膜。S02. The mixed solution is deposited on the surface of the substrate and dried to form a film.
本申请实施例提供的薄膜的制备方法，将石墨烯和纳米氧化锌按照用量比分散在有机溶剂中，混合后超声分散，将得到的混合溶液沉积在待沉积薄膜的目标基底表面，经干燥处理即可得到。该方法不仅方法简单，易于操作，而且得到的薄膜用作发光二极管的电子传输层时，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。In the method for preparing a thin film provided in the examples of the present application, graphene and nano-zinc oxide are dispersed in an organic solvent according to the amount ratio, and after mixing, they are ultrasonically dispersed, and the resulting mixed solution is deposited on the target substrate surface of the thin film to be deposited, and dried To get it. This method is not only simple and easy to operate, but when the resulting thin film is used as an electron transport layer of a light emitting diode, it can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
具体的，上述步骤S01中，本申请实施例中，所述纳米氧化锌和所述石墨烯均可以参考现有方法制备获得。Specifically, in the above step S01, in the embodiments of the present application, both the nano-zinc oxide and the graphene can be prepared by reference to existing methods.
作为一个实施例，所述氧化锌的制备方法为：将醋酸锌溶于二甲亚砜，将四甲基氢氧化铵溶于乙醇，然后混合处理，在室温下搅拌反应；反应结束后加入乙酸乙酯，离心处理后去除上层清液；在收集的沉淀物中后加入乙醇胺和乙醇稳定纳米颗粒，再用乙酸乙酯清洗，离心去除上清液，干燥后得到ZnO纳米颗粒。在一些实施例中，将醋酸锌与二甲亚砜按质量体积比为1g:60ml，将醋酸锌溶于二甲亚砜，将四甲基氢氧化铵与乙醇按照质量体积比为1.0 g：10ml，将四甲基氢氧化铵溶于乙醇，然后混合处理，在室温反应下搅拌24小时；反应结束后加入乙酸乙酯，在转速为8000rpm的条件下离心10min，去除上层清液，按照醋酸锌和乙醇胺的质量体积比为1g:1ml、醋酸锌和乙醇的质量体积比为1g:10ml的比例，在沉淀物中加入乙醇胺和乙醇稳定纳米颗粒，再用乙酸乙酯清洗，在转速为8000rpm的条件下离心10min ，去除上清液，干燥后得到ZnO纳米颗粒，最后溶于适量乙醇中。As an example, the preparation method of zinc oxide is: dissolving zinc acetate in dimethyl sulfoxide, dissolving tetramethyl ammonium hydroxide in ethanol, and then mixing and processing, stirring the reaction at room temperature; adding acetic acid after the reaction Ethyl acetate, remove the supernatant after centrifugation; add ethanolamine and ethanol to stabilize the nanoparticles after collecting the precipitate, then wash with ethyl acetate, centrifuge to remove the supernatant, and dry to obtain ZnO nanoparticles. In some embodiments, the mass ratio of zinc acetate to dimethyl sulfoxide is 1 g: 60 ml, the zinc acetate is dissolved in dimethyl sulfoxide, and the mass ratio of tetramethyl ammonium hydroxide to ethanol is 1.0 g: 10ml, dissolve tetramethylammonium hydroxide in ethanol, then mix and process, stir at room temperature for 24 hours; add ethyl acetate after the reaction, centrifuge at 8000rpm for 10min, remove the supernatant, follow the acetic acid The mass-volume ratio of zinc and ethanolamine is 1g: 1ml, and the mass-volume ratio of zinc acetate and ethanol is 1g: 10ml. Add ethanolamine and ethanol to the precipitate to stabilize the nanoparticles, and then wash with ethyl acetate at a speed of 8000rpm After centrifuging for 10 min under the conditions, the supernatant was removed, dried to obtain ZnO nanoparticles, and finally dissolved in an appropriate amount of ethanol.
作为一个实施例，所述石墨烯的制备方法为：利用hummer法制备氧化石墨烯，再用水合肼还原氧化石墨烯得到石墨烯。As an example, the method for preparing graphene is: using a hummer method to prepare graphene oxide, and then reducing the graphene oxide with hydrazine hydrate to obtain graphene.
按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，可以通过多种方法实现。According to the ratio of graphene to the total weight of graphene and nano-zinc oxide of 0.1% to 10%, dispersing nano-zinc oxide and graphene in an organic solvent can be achieved by various methods.
在一些实施例中，分别提供石墨烯的有机溶液和纳米氧化锌的有机溶液，按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将石墨烯的有机溶液和纳米氧化锌的有机溶液进行混合。其中，所述石墨烯的有机溶液中的溶剂可以采用能够有效分散石墨烯的有机溶剂，在一些实施例中为有机醇类；所述纳米氧化锌的有机溶液中的溶剂为能有效分散纳米氧化锌和石墨烯的有机溶剂，在一些实施例中为有机醇类。在一些实施例中，石墨烯的有机溶液中的溶剂和纳米氧化锌的有机溶液中的溶剂均为乙醇。In some embodiments, an organic solution of graphene and an organic solution of nano-zinc oxide are provided separately. According to a ratio of 0.1% to 10% of the total weight of graphene and nano-zinc oxide, the organic solution and nano-graphene of graphene The organic solution of zinc oxide is mixed. Wherein, the solvent in the organic solution of graphene can be an organic solvent that can effectively disperse graphene, in some embodiments, organic alcohols; the solvent in the organic solution of nano-zinc oxide can effectively disperse nano-oxide The organic solvents of zinc and graphene are, in some embodiments, organic alcohols. In some embodiments, the solvent in the organic solution of graphene and the solvent in the organic solution of nano-zinc oxide are both ethanol.
在一些实施例中，分别提供石墨烯和纳米氧化锌，将所述石墨烯和纳米氧化锌分散在有机溶剂中，进行混合处理。其中，所述有机溶剂为能同时有效分散纳米氧化锌和石墨烯的有机溶剂，在一些实施例中为有机醇类，在一些实施例中为乙醇。In some embodiments, graphene and nano-zinc oxide are provided separately, and the graphene and nano-zinc oxide are dispersed in an organic solvent and subjected to mixing treatment. Wherein, the organic solvent is an organic solvent that can effectively disperse nano-zinc oxide and graphene at the same time, in some embodiments, organic alcohols, and in some embodiments, ethanol.
将所述纳米氧化锌和石墨烯分散在有机溶剂中后，混合处理。为了使得两者分散均匀，将得到的分散体系进行超声处理。在一些实施例中，在自然状态下超声4h~6h，得到混合溶液。After dispersing the nano-zinc oxide and graphene in an organic solvent, they are mixed and processed. In order to make the two dispersed evenly, the obtained dispersion system was sonicated. In some embodiments, ultrasound is performed in a natural state for 4 to 6 hours to obtain a mixed solution.
上述步骤S02中，将所述混合溶液沉积在基底表面，可以采用常规的溶液加工法实现，如喷墨打印、旋涂等。进一步的，经过干燥处理成膜。其中，所述基底为需要沉积所述混合溶液的任何基底，特别的，当所述纳米氧化锌和石墨烯的复合材料作为量子点发光二极管的电子传输层材料时，所述基底可以为层叠有阳极/量子点发光层的叠层、阳极/空穴功能层/量子点发光层的叠层、阴极、阴极/电子注入层的叠层。In the above step S02, depositing the mixed solution on the surface of the substrate can be achieved by a conventional solution processing method, such as inkjet printing, spin coating, and the like. Further, the film is formed after drying treatment. Wherein, the substrate is any substrate that needs to deposit the mixed solution. In particular, when the composite material of nano-zinc oxide and graphene is used as the electron transport layer material of the quantum dot light emitting diode, the substrate may be laminated Anode/quantum dot light emitting layer stack, anode/hole function layer/quantum dot light emitting layer stack, cathode, cathode/electron injection layer stack.
在一些实施例中，将所述混合溶液沉积在基底表面，制备沿着垂直膜层的方向，石墨烯梯度分布的薄膜。In some embodiments, the mixed solution is deposited on the surface of the substrate to prepare a thin film with graphene gradient distribution along the direction perpendicular to the film layer.
在一些实施例中，将所述混合溶液沉积在基底表面，干燥成膜的方法为：In some embodiments, the mixed solution is deposited on the surface of the substrate, and the method of drying the film is:
S021. 将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于可加热装置中，其中，所述可加热装置包括相对且平行设置的底板和顶板，且所述沉积有所述混合溶液的基底平行于所述底板放置在所述可密闭装置中；S021. The mixed solution is deposited on the surface of the substrate, and the substrate on which the mixed solution is deposited is placed in a heatable device, wherein the heatable device includes a bottom plate and a top plate that are opposed and arranged in parallel, and the deposited The base of the mixed solution is placed in the sealable device parallel to the bottom plate;
S022. 对所述可密闭装置进行加热处理。S022. Heat-treating the sealable device.
该方法中，将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于具有特定结构的可加热装置，通过调控加热条件实现石墨烯在膜层中的梯度分布。具体的，所述可加热装置包括相对且平行设置的底板和顶板，且所述沉积有所述混合溶液的基底平行于所述底板放置在所述可密闭装置中。In this method, the mixed solution is deposited on the surface of the substrate, the substrate deposited with the mixed solution is placed in a heatable device with a specific structure, and the gradient distribution of graphene in the film layer is achieved by adjusting the heating conditions. Specifically, the heatable device includes a bottom plate and a top plate that are opposed and parallel, and the substrate on which the mixed solution is deposited is placed in the sealable device parallel to the bottom plate.
在一些实施例中，对所述可密闭装置进行加热处理的步骤中，所述可加热装置中，所述底板的温度为60℃~80℃，所述顶板的温度为80℃~120℃，且所述底板和所述顶板的温度差大于等于20℃。在该加热条件下形成温度梯度，在温度梯度的驱动下，通过物理吸附负载在石墨烯上的氧化锌纳米颗粒会形成从顶部（靠近所述顶板的一侧）向底部（靠近所述顶板的一侧）的运动，最终干燥后形成顶部纳米氧化锌浓度低、底部纳米氧化锌浓度高的复合石墨烯/ZnO的薄膜。由于溶液本身容易倾向于形成表面能较低的状态，石墨烯更倾向于暴露在表面，而在温度梯度存在的情况下，会加速氧化锌纳米颗的运动，更有利于形成具有浓度梯度的薄膜。In some embodiments, in the step of heating the sealable device, in the heatable device, the temperature of the bottom plate is 60°C to 80°C, and the temperature of the top plate is 80°C to 120°C. And the temperature difference between the bottom plate and the top plate is greater than or equal to 20°C. Under this heating condition, a temperature gradient is formed. Under the driving of the temperature gradient, the zinc oxide nanoparticles supported on the graphene by physical adsorption will form from the top (side close to the top plate) to the bottom (close to the top plate) One side) movement, after drying, a composite graphene/ZnO thin film with a low nano zinc oxide concentration on the top and a high nano zinc oxide concentration on the bottom is formed. Since the solution itself tends to form a state with lower surface energy, graphene tends to be exposed on the surface, and in the presence of a temperature gradient, it will accelerate the movement of zinc oxide nanoparticles, which is more conducive to the formation of a thin film with a concentration gradient .
在一些实施例中，所述沉积有所述混合溶液的基底不与所述可加热装置的底板、顶板直接接触，从而有利于在较薄的膜层中形成明显的温度梯度。在一些实施例中，以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基底置于h/3~2h/3之间，从而有利于形成相对均匀且平缓的温度梯度，有利于得到的膜层中的石墨烯浓度的平缓变化，最终更有利于在有效利用石墨烯钝化ZnO，减少ZnO表面缺陷态对激子的淬灭的同时，避免由于过度降低ZnO的费米能级带来的器件电荷不平衡的现象，最终有效提升器件的发光效率。In some embodiments, the substrate on which the mixed solution is deposited does not directly contact the bottom plate and the top plate of the heatable device, thereby facilitating the formation of a significant temperature gradient in the thin film layer. In some embodiments, based on the height between the bottom plate and the top plate as h, the substrate on which the mixed solution is deposited is placed between h/3~2h/3, thereby facilitating the formation of a relatively uniform And the gentle temperature gradient is conducive to the gentle change of the graphene concentration in the obtained film layer, and finally it is more conducive to effectively use graphene to passivate ZnO, reduce the quenching of excitons on the surface defect state of ZnO, and avoid due to Excessively reducing the device charge imbalance caused by the Fermi level of ZnO effectively improves the luminous efficiency of the device.
在一些实施例中，将所述混合溶液沉积在基底表面，干燥成膜的方法为：In some embodiments, the mixed solution is deposited on the surface of the substrate, and the method of drying the film is:
将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于热板上，在所述热板外接正电压的条件下进行加热处理，制备薄膜。The mixed solution is deposited on the surface of the substrate, the substrate on which the mixed solution is deposited is placed on a hot plate, and heat treatment is performed under the condition that the hot plate is connected with a positive voltage to prepare a thin film.
在一些实施例中，该方法中，在所述热板外接正电压的条件下进行加热处理的步骤，在温度为80~120℃的条件下进行。由于混合溶液中的纳米氧化锌颗粒表面通常会有羟基，显负电，因此，在静电吸附的驱动下，负载在石墨烯上的纳米氧化锌颗粒会形成从顶部向底部的运动，最终干燥后形成顶部纳米氧化锌浓度低、底部纳米氧化锌浓度高的复合石墨烯/ZnO的薄膜。In some embodiments, in this method, the step of performing the heat treatment under the condition that the hot plate is connected with a positive voltage is performed under the condition that the temperature is 80 to 120°C. Since the surface of the nano-zinc oxide particles in the mixed solution usually has hydroxyl groups, which is negatively charged, under the drive of electrostatic adsorption, the nano-zinc oxide particles loaded on the graphene will form a movement from the top to the bottom, and finally form after drying A thin film of composite graphene/ZnO with a low nano zinc oxide concentration on the top and a high nano zinc oxide concentration on the bottom.
如图1所示，本申请实施例还提供了一种量子点发光二极管，包括相对设置的阳极1和阴极6，设置在阳极1和阴极6之间的量子点发光层4，以及设置在阴极6和量子点发光层4之间的电子传输层5，其中，电子传输层5的材料为本申请实施例所述的复合材料，或电子传输层5为本申请实施例所述的薄膜。As shown in FIG. 1, an embodiment of the present application further provides a quantum dot light-emitting diode, including an anode 1 and a cathode 6 disposed oppositely, a quantum dot light-emitting layer 4 disposed between the anode 1 and the cathode 6, and a cathode disposed 6 and the electron transport layer 5 between the quantum dot light emitting layer 4, wherein the material of the electron transport layer 5 is the composite material described in the embodiments of the present application, or the electron transport layer 5 is the thin film described in the embodiments of the present application.
本申请实施例提供的量子点发光二极管，包括电子传输层，所述电子传输层的材料为上述纳米氧化锌和石墨烯的复合材料。由此得到的量子点发光二极管，可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。The quantum dot light emitting diode provided by the embodiment of the present application includes an electron transport layer, and the material of the electron transport layer is a composite material of the above-mentioned nano zinc oxide and graphene. The quantum dot light-emitting diode thus obtained can effectively prevent electrons from further transmitting to the valence band of the quantum dot, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
在一些实施例中，从量子点发光层4到阴极6的方向，电子传输层5中的石墨烯的含量渐增。此时，靠近量子点发光层4的一端ZnO浓度较高，对应地，石墨烯浓度低，由此形成的薄膜，能够有效利用石墨烯钝化ZnO，减少ZnO表面缺陷态对激子的淬灭，同时，避免由于过度降低ZnO的费米能级带来的器件电荷不平衡的现象，最终有效提升器件的发光效率。In some embodiments, the content of graphene in the electron transport layer 5 gradually increases from the direction of the quantum dot light-emitting layer 4 to the cathode 6. At this time, the concentration of ZnO at the end close to the quantum dot light-emitting layer 4 is high, and correspondingly, the concentration of graphene is low. The thin film formed thereby can effectively use graphene to passivate ZnO and reduce the quenching of excitons by defect states on the surface of ZnO At the same time, to avoid the device charge imbalance caused by excessively reducing the Fermi level of ZnO, and ultimately effectively improve the luminous efficiency of the device.
具体的，所述量子点发光二极管还包括衬底0，衬底0可以设置在阳极1一端，形成正置量子点发光二极管；衬底0可以设置在阴极6一端，形成倒置量子点发光二极管。Specifically, the quantum dot light emitting diode further includes a substrate 0. The substrate 0 may be disposed at the end of the anode 1 to form an upright quantum dot light emitting diode; the substrate 0 may be disposed at the end of the cathode 6 to form an inverted quantum dot light emitting diode.
在一些实施例中，所述量子点发光二极管还包括设置在阳极1和量子点发光层4之间的空穴功能层、空穴注入层中的至少一层。在一些实施例中，所述量子点发光二极管包括设置在阳极1和量子点发光层4之间的空穴功能层2。在一些实施例中，所述量子点发光二极管包括设置在阳极1和量子点发光层4之间的空穴注入层3。在一些实施例中，所述量子点发光二极管包括设置在阳极1和量子点发光层4之间的空穴功能层2，以及设置在空穴传输层2和量子点发光层4之间的空穴注入层3。In some embodiments, the quantum dot light emitting diode further includes at least one of a hole functional layer and a hole injection layer disposed between the anode 1 and the quantum dot light emitting layer 4. In some embodiments, the quantum dot light emitting diode includes a hole function layer 2 disposed between the anode 1 and the quantum dot light emitting layer 4. In some embodiments, the quantum dot light emitting diode includes a hole injection layer 3 disposed between the anode 1 and the quantum dot light emitting layer 4. In some embodiments, the quantum dot light emitting diode includes a hole function layer 2 disposed between the anode 1 and the quantum dot light emitting layer 4, and a space disposed between the hole transport layer 2 and the quantum dot light emitting layer 4 Hole injection layer 3.
在一些实施例中，所述量子点发光二极管还包括设置在阴极6和电子传输层5之间的电子注入层（图中未标出）。In some embodiments, the quantum dot light emitting diode further includes an electron injection layer (not shown in the figure) disposed between the cathode 6 and the electron transport layer 5.
相应的，本申请实施例提供了一种量子点发光二极管的制备方法，包括以下步骤：Correspondingly, the embodiments of the present application provide a method for manufacturing a quantum dot light emitting diode, including the following steps:
按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；According to the ratio of graphene to the total weight of graphene and nano-zinc oxide 0.1%~10%, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
提供第一基板，将所述混合溶液沉积在所述第一基板表面，干燥成膜，制备电子传输层。A first substrate is provided, the mixed solution is deposited on the surface of the first substrate, dried to form a film, and an electron transport layer is prepared.
本申请实施例提供的量子点发光二极管的制备方法，将石墨烯和纳米氧化锌按照用量比分散在有机溶剂中，混合后超声分散，将得到的混合溶液沉积在待沉积薄膜的第一基底表面，经干燥处理即可得到电子传输层。该方法不仅方法简单，易于操作，而且得到的电子传输层可以有效避免电子进一步传输到量子点的价带，减少激子淬灭几率，提高器件发光效率。The preparation method of the quantum dot light-emitting diode provided in the embodiment of the present application disperses graphene and nano-zinc oxide in an organic solvent according to the amount ratio, and after mixing, disperses ultrasonically to deposit the resulting mixed solution on the surface of the first substrate of the thin film to be deposited After drying, the electron transport layer can be obtained. The method is not only simple and easy to operate, but also the obtained electron transport layer can effectively prevent electrons from further transmitting to the valence band of quantum dots, reduce the probability of exciton quenching, and improve the luminous efficiency of the device.
本申请实施例中，在所述第一基板表面制备电子传输层的步骤及其优选情形，如上文所述，为了节约篇幅，此处不再赘述。In the embodiment of the present application, the steps for preparing the electron transport layer on the surface of the first substrate and the preferred situations thereof are as described above. In order to save space, they will not be repeated here.
作为一种实施情形，所述第一基板包括阳极，在所述阳极上设置的量子点发光层。在一些实施例中，所述第一基板还包括设置在所述阳极和所述量子点发光层之间的空穴功能层。其中，所述空穴功能层包括但不限于空穴注入层、空穴传输层、电子阻挡层中的至少一层。在一些实施例中，所述阳极为设置在衬底上的阳极。As an implementation situation, the first substrate includes an anode, and a quantum dot light emitting layer provided on the anode. In some embodiments, the first substrate further includes a hole function layer disposed between the anode and the quantum dot light emitting layer. Wherein, the hole functional layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer. In some embodiments, the anode is an anode disposed on the substrate.
进一步的，在制备往所述电子传输层之后，还包括在所述电子传输层背离所述量子点发光层的表面制备阴极。在一些实施例中，在制备阴极之前，还包括在电子传输层背离所述量子点发光层的表面制备电子注入层。Further, after preparing the electron transport layer, it further includes preparing a cathode on the surface of the electron transport layer facing away from the quantum dot light emitting layer. In some embodiments, before preparing the cathode, it further includes preparing an electron injection layer on the surface of the electron transport layer facing away from the quantum dot light emitting layer.
作为另一种实施情形，所述第一基板为阴极。在一些实施例中，所述阴极为设置在衬底上的阴极。在一些实施例中，在制备往所述电子传输层之前，还包括在所述阴极上制备电子注入层。As another implementation situation, the first substrate is a cathode. In some embodiments, the cathode is a cathode provided on a substrate. In some embodiments, before preparing the electron transport layer, the method further includes preparing an electron injection layer on the cathode.
进一步的，在制备往所述电子传输层之后，还包括在所述电子传输层背离所述阴极的表面制备量子点发光层，在所述量子点发光层背离所述阴极的表面制备阳极。在一些实施例中，在制备阳极之前，还包括在量子点发光层背离所述阴极的表面制备空穴功能层。其中，所述空穴功能层包括但不限于空穴注入层、空穴传输层、电子阻挡层中的至少一层。Further, after preparing the electron transport layer, the method further includes preparing a quantum dot light-emitting layer on the surface of the electron transport layer facing away from the cathode, and preparing an anode on the surface of the quantum dot light-emitting layer facing away from the cathode. In some embodiments, before preparing the anode, it further includes preparing a hole function layer on the surface of the quantum dot light-emitting layer facing away from the cathode. Wherein, the hole functional layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
下面结合具体实施例进行说明。The following is a description with reference to specific embodiments.
实施例1Example 1
一种量子点发光二极管，包括衬底，设置在所述衬底上的阳极和阴极，设置在所述阳极和阴极之间的叠层结构，所述叠层结构包括层叠结合的空穴注入层-空穴传输层-量子点发光层-电子传输层，其中，空穴注入层邻近所述阳极设置，所述电子传输层邻近所述阴极设置。A quantum dot light-emitting diode includes a substrate, an anode and a cathode provided on the substrate, and a laminated structure provided between the anode and the cathode, the laminated structure includes a layered hole injection layer -A hole transport layer-a quantum dot light emitting layer-an electron transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the electron transport layer is disposed adjacent to the cathode.
所述量子点发光二极管的制备方法，包括以下步骤：The preparation method of the quantum dot light-emitting diode includes the following steps:
在阳极基板上沉积空穴注入层，在空穴注入层上沉积空穴传输层，在空穴传输层上沉积量子点发光层；Deposit a hole injection layer on the anode substrate, deposit a hole transport layer on the hole injection layer, and deposit a quantum dot light-emitting layer on the hole transport layer;
将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于可加热装置中，其中，所述可加热装置包括相对且平行设置的底板和顶板，且所述沉积有所述混合溶液的基板平行于所述底板放置在所述可密闭装置中。对所述可密闭装置进行加热处理，使得底板的加热温度60℃，顶板的加热温度80℃，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层；The graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, and is placed in a heatable device, wherein the heatable device includes a bottom plate and a top plate that are opposite and arranged in parallel, and the mixture is deposited The substrate of the solution is placed in the sealable device parallel to the bottom plate. Heat-treating the sealable device so that the heating temperature of the bottom plate is 60°C and the heating temperature of the top plate is 80°C, and after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed;
在电子传输层上沉积阴极，封装后完成器件制备。The cathode is deposited on the electron transport layer, and the device preparation is completed after packaging.
实施例2Example 2
与实施例1的不同之处在于，底板的加热温度60℃，顶板的加热温度100℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 60° C., the heating temperature of the top plate is 100° C., and the height between the bottom plate and the top plate is h. The substrate is placed between h/3~2h/3.
实施例3Example 3
与实施例1的不同之处在于，底板的加热温度60℃，顶板的加热温度120℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 60° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h. The substrate is placed between h/3~2h/3.
实施例4Example 4
与实施例1的不同之处在于，底板的加热温度70℃，顶板的加热温度90℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 90° C., and the height between the bottom plate and the top plate is calculated as h. The substrate is placed between h/3~2h/3.
实施例5Example 5
与实施例1的不同之处在于，底板的加热温度70℃，顶板的加热温度105℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 105° C., and the height between the bottom plate and the top plate is h, and the mixed solution deposited The substrate is placed between h/3~2h/3.
实施例5Example 5
与实施例1的不同之处在于，底板的加热温度70℃，顶板的加热温度120℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 70° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h. The substrate is placed between h/3~2h/3.
实施例6Example 6
与实施例1的不同之处在于，底板的加热温度80℃，顶板的加热温度120℃，且以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基板置于h/3~2h/3之间。The difference from Example 1 is that the heating temperature of the bottom plate is 80° C., the heating temperature of the top plate is 120° C., and the height between the bottom plate and the top plate is h. The substrate is placed between h/3~2h/3.
实施例7Example 7
一种量子点发光二极管，包括衬底，设置在所述衬底上的阳极和阴极，设置在所述阳极和阴极之间的叠层结构，所述叠层结构包括层叠结合的空穴注入层-空穴传输层-量子点发光层-电子传输层，其中，空穴注入层邻近所述阳极设置，所述电子传输层邻近所述阴极设置。A quantum dot light-emitting diode includes a substrate, an anode and a cathode provided on the substrate, and a laminated structure provided between the anode and the cathode, the laminated structure includes a layered hole injection layer -A hole transport layer-a quantum dot light emitting layer-an electron transport layer, wherein the hole injection layer is disposed adjacent to the anode, and the electron transport layer is disposed adjacent to the cathode.
所述量子点发光二极管的制备方法，包括以下步骤：The preparation method of the quantum dot light-emitting diode includes the following steps:
在阳极基板上沉积空穴注入层，在空穴注入层上沉积空穴传输层，在空穴传输层上沉积量子点发光层；Deposit a hole injection layer on the anode substrate, deposit a hole transport layer on the hole injection layer, and deposit a quantum dot light-emitting layer on the hole transport layer;
将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于热板上，在所述热板外接正电压、在温度为80℃的条件下加热，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层；The graphene/ZnO composite material solution was spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and the positive temperature of the external plate was heated at a temperature of 80° C. After drying, the top ZnO concentration was low after drying 1. Electron transport layer of composite graphene/ZnO with high ZnO concentration at the bottom;
在电子传输层上沉积阴极，封装后完成器件制备。The cathode is deposited on the electron transport layer, and the device preparation is completed after packaging.
实施例8Example 8
与实施例2的不同之处在于，将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于热板上，在所述热板外接正电压、在温度为90℃的条件下加热，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层。The difference from Example 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and a positive voltage is connected to the hot plate at a temperature of 90°C Under heating, after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed.
实施例9Example 9
与实施例2的不同之处在于，将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于热板上，在所述热板外接正电压、在温度为100℃的条件下加热，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层。The difference from Example 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and a positive voltage is connected to the hot plate at a temperature of 100°C Under heating, after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed.
实施例10Example 10
与实施例2的不同之处在于，将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于热板上，在所述热板外接正电压、在温度为110℃的条件下加热，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层。The difference from Example 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and a positive voltage is connected to the hot plate at a temperature of 110°C Under heating, after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed.
实施例11Example 11
与实施例2的不同之处在于，将石墨烯/ZnO的复合材料溶液旋涂在量子点发光层上，置于热板上，在所述热板外接正电压、在温度为120℃的条件下加热，干燥后形成顶部ZnO浓度低、底部ZnO浓度高的复合石墨烯/ZnO的电子传输层。The difference from Example 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, and a positive voltage is connected to the hot plate at a temperature of 120°C Under heating, after drying, a composite graphene/ZnO electron transport layer with a low ZnO concentration at the top and a high ZnO concentration at the bottom is formed.
以上所述实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围，均应包含在本申请的保护范围之内。The above-mentioned embodiments are only used to illustrate the technical solutions of the present application, not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, persons of ordinary skill in the art should understand that they can still implement the foregoing The technical solutions described in the examples are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not deviate from the spirit and scope of the technical solutions of the embodiments of the present application. Within the scope of protection of this application.

Claims (20)

  1. 一种复合材料，其特征在于，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。A composite material, characterized in that the composite material is nano-zinc oxide and graphene, and based on the total weight of the composite material is 100%, the weight percentage of the graphene is 0.1% to 10% .
  2. 如权利要求1所述的复合材料，其特征在于，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为3%~10%。The composite material according to claim 1, wherein the weight percentage of the graphene is 3% to 10% based on the total weight of the composite material being 100%.
  3. 一种薄膜，其特征在于，所述薄膜的材料包括复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。A film, characterized in that the material of the film includes a composite material, the composite material is nano-zinc oxide and graphene, and the total weight of the graphene is 100% based on the total weight of the composite material being 100% The content is 0.1%~10%.
  4. 如权利要求3所述的薄膜，其特征在于，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为3%~10%。The thin film according to claim 3, wherein the weight percentage of the graphene is 3% to 10% based on the total weight of the composite material being 100%.
  5. 如权利要求3所述的薄膜，其特征在于，所述薄膜中，所述石墨烯的重量百分含量沿着垂直于所述薄膜的方向梯度分布。The thin film according to claim 3, wherein the weight percentage of the graphene in the thin film is distributed along a gradient perpendicular to the thin film.
  6. 一种薄膜的制备方法，其特征在于，包括以下步骤：A method for preparing a film, which is characterized by comprising the following steps:
    按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；According to the ratio of graphene to the total weight of graphene and nano-zinc oxide 0.1%~10%, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
    将所述混合溶液沉积在基底表面，干燥成膜。The mixed solution is deposited on the surface of the substrate and dried to form a film.
  7. 如权利要求6所述的薄膜的制备方法，其特征在于，将所述混合溶液沉积在基底表面，干燥成膜的方法为：The method for preparing a thin film according to claim 6, wherein the method for depositing the mixed solution on the surface of the substrate and drying the film is:
    将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于可加热装置中，其中，所述可加热装置包括相对且平行设置的底板和顶板，且所述沉积有所述混合溶液的基底平行于所述底板放置在所述可密闭装置中；Depositing the mixed solution on the surface of the substrate, and placing the substrate on which the mixed solution is deposited in a heatable device, wherein the heatable device includes a bottom plate and a top plate that are opposite and arranged in parallel, and the deposited The base of the mixed solution is placed in the sealable device parallel to the bottom plate;
    对所述可密闭装置进行加热处理。Heat-treating the sealable device.
  8. 如权利要求7所述的薄膜的制备方法，其特征在于，对所述可密闭装置进行加热处理的步骤中，所述可加热装置中，所述底板的温度为60℃~80℃，所述顶板的温度为80℃~120℃，且所述底板和所述顶板的温度差大于等于20℃。The method for preparing a thin film according to claim 7, wherein in the step of performing heat treatment on the sealable device, in the heatable device, the temperature of the bottom plate is 60°C to 80°C. The temperature of the top plate is 80°C to 120°C, and the temperature difference between the bottom plate and the top plate is greater than or equal to 20°C.
  9. 如权利要求7所述的薄膜的制备方法，其特征在于，将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于可加热装置中的步骤中，所述沉积有所述混合溶液的基底不与所述可加热装置的底板、顶板直接接触。The method for preparing a thin film according to claim 7, wherein the step of depositing the mixed solution on the surface of the substrate and placing the substrate on which the mixed solution is deposited in a heatable device The base of the mixed solution does not directly contact the bottom plate and the top plate of the heatable device.
  10. 如权利要求7所述的薄膜的制备方法，其特征在于，以所述底板和所述顶板之间的高度为h计，所述沉积有所述混合溶液的基底置于h/3~2h/3之间。The method for preparing a thin film according to claim 7, characterized in that, based on the height between the bottom plate and the top plate as h, the substrate on which the mixed solution is deposited is placed at h/3~2h/ Between 3.
  11. 如权利要求6所述的薄膜的制备方法，其特征在于，将所述混合溶液沉积在基底表面，干燥成膜的方法为：The method for preparing a thin film according to claim 6, wherein the method for depositing the mixed solution on the surface of the substrate and drying the film is:
    将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于热板上，在所述热板外接正电压的条件下进行加热处理，制备薄膜。The mixed solution is deposited on the surface of the substrate, the substrate on which the mixed solution is deposited is placed on a hot plate, and heat treatment is performed under the condition that the hot plate is connected with a positive voltage to prepare a thin film.
  12. 如权利要求11所述的薄膜的制备方法，其特征在于，在所述热板外接正电压的条件下进行加热处理的步骤，在温度为80~120℃的条件下进行。The method for preparing a thin film according to claim 11, wherein the step of performing the heat treatment under the condition that the hot plate is connected with a positive voltage is performed under the condition of a temperature of 80 to 120°C.
  13. 一种量子点发光二极管，其特征在于，包括相对设置的阳极和阴极，设置在所述阳极和所述阴极之间的量子点发光层，以及设置在所述阴极和所述量子点发光层之间的电子传输层，其中，所述电子传输层的材料为复合材料，所述复合材料为纳米氧化锌和石墨烯，且以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为0.1%~10%。A quantum dot light-emitting diode, characterized in that it includes an anode and a cathode arranged oppositely, a quantum dot light-emitting layer arranged between the anode and the cathode, and one of the cathode and the quantum dot light-emitting layer Between the electron transport layer, wherein the material of the electron transport layer is a composite material, the composite material is nano zinc oxide and graphene, and based on the total weight of the composite material is 100%, the graphene The weight percentage is 0.1%~10%.
  14. 如权利要求13所述的量子点发光二极管，其特征在于，以所述复合材料的总重量为100%计，所述石墨烯的重量百分含量为3%~10%。The quantum dot light emitting diode according to claim 13, wherein the weight percentage of the graphene is 3% to 10% based on the total weight of the composite material being 100%.
  15. 如权利要求13所述的量子点发光二极管，其特征在于，从所述量子点发光层到所述阴极的方向，所述电子传输层中的石墨烯的含量渐增。The quantum dot light-emitting diode according to claim 13, wherein the content of graphene in the electron transport layer gradually increases from the quantum dot light-emitting layer to the cathode.
  16. 一种量子点发光二极管的制备方法，其特征在于，包括以下步骤：A preparation method of quantum dot light-emitting diode, which is characterized by comprising the following steps:
    按照石墨烯占石墨烯和纳米氧化锌总重量的0.1%~10%的比例，将纳米氧化锌和石墨烯分散在有机溶剂中，混合后进行超声处理，得到混合溶液；According to the ratio of graphene to the total weight of graphene and nano-zinc oxide 0.1%~10%, nano-zinc oxide and graphene are dispersed in an organic solvent, mixed and then subjected to ultrasonic treatment to obtain a mixed solution;
    提供第一基板，将所述混合溶液沉积在所述第一基板表面，干燥成膜，制备电子传输层。A first substrate is provided, the mixed solution is deposited on the surface of the first substrate, dried to form a film, and an electron transport layer is prepared.
  17. 如权利要求16所述的量子点发光二极管的制备方法，其特征在于，将所述混合溶液沉积在基底表面，干燥成膜的方法为：The method for preparing a quantum dot light emitting diode according to claim 16, wherein the method of depositing the mixed solution on the surface of the substrate and drying to form a film is:
    将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于可加热装置中，其中，所述可加热装置包括相对且平行设置的底板和顶板，且所述沉积有所述混合溶液的基底平行于所述底板放置在所述可密闭装置中；Depositing the mixed solution on the surface of the substrate, and placing the substrate on which the mixed solution is deposited in a heatable device, wherein the heatable device includes a bottom plate and a top plate that are opposite and arranged in parallel, and the deposited The base of the mixed solution is placed in the sealable device parallel to the bottom plate;
    对所述可密闭装置进行加热处理。Heat-treating the sealable device.
  18. 如权利要求17所述的量子点发光二极管的制备方法，其特征在于，对所述可密闭装置进行加热处理的步骤中，所述可加热装置中，所述底板的温度为60℃~80℃，所述顶板的温度为80℃~120℃，且所述底板和所述顶板的温度差大于等于20℃。The method for preparing a quantum dot light emitting diode according to claim 17, wherein in the step of heating the sealable device, in the heatable device, the temperature of the bottom plate is 60°C to 80°C The temperature of the top plate is 80°C~120°C, and the temperature difference between the bottom plate and the top plate is greater than or equal to 20°C.
  19. 如权利要求16所述的量子点发光二极管的制备方法，其特征在于，将所述混合溶液沉积在基底表面，干燥成膜的方法为：The method for preparing a quantum dot light emitting diode according to claim 16, wherein the method of depositing the mixed solution on the surface of the substrate and drying to form a film is:
    将所述混合溶液沉积在基底表面，将沉积有所述混合溶液的基底置于热板上，在所述热板外接正电压的条件下进行加热处理，制备薄膜。The mixed solution is deposited on the surface of the substrate, the substrate on which the mixed solution is deposited is placed on a hot plate, and heat treatment is performed under the condition that the hot plate is connected with a positive voltage to prepare a thin film.
  20. 如权利要求19所述的量子点发光二极管的制备方法，其特征在于，在所述热板外接正电压的条件下进行加热处理的步骤，在温度为80~120℃的条件下进行。The method of manufacturing a quantum dot light emitting diode according to claim 19, wherein the step of performing the heat treatment under the condition that the hot plate is connected with a positive voltage is performed under the condition of a temperature of 80 to 120°C.
PCT/CN2019/108154 2018-12-28 2019-09-26 Composite material, thin film and preparing method therefor and quantum dot light-emitting diode WO2020134252A1 (en)

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