WO2020258468A1 - 一种钙钛矿型电致发光器件及其制备方法 - Google Patents

一种钙钛矿型电致发光器件及其制备方法 Download PDF

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WO2020258468A1
WO2020258468A1 PCT/CN2019/101465 CN2019101465W WO2020258468A1 WO 2020258468 A1 WO2020258468 A1 WO 2020258468A1 CN 2019101465 W CN2019101465 W CN 2019101465W WO 2020258468 A1 WO2020258468 A1 WO 2020258468A1
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transport layer
hole transport
layer
perovskite
electroluminescent device
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PCT/CN2019/101465
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English (en)
French (fr)
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江沛
李佳育
徐君哲
陈书志
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深圳市华星光电半导体显示技术有限公司
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Priority to US16/617,599 priority Critical patent/US20210336175A1/en
Publication of WO2020258468A1 publication Critical patent/WO2020258468A1/zh

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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
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • 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
    • 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
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • 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
    • 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

Definitions

  • the invention relates to the technical field of display panels, in particular to a perovskite type electroluminescent device and a preparation method thereof.
  • Perovskite material (ABX3) has excellent photoelectric properties, adjustable band gap, solution preparation, and low cost.
  • A is methylamine (MA+), formamidine (FA+), cesium (Cs+) or organic macromolecules Etc.
  • B is lead (Pb2+), tin (Sn2+), etc.
  • X is halogen chloride (Cl-), bromine (Br-), iodine (I-), etc.
  • the photoelectric conversion efficiency of perovskite materials in the field of solar cells has reached 23.7%, which exceeds that of traditional silicon-based solar cells.
  • its stability problem is gradually being solved, and it has considerable commercial prospects.
  • perovskite materials in the display field PeLED
  • perovskite materials in the display field PeLED
  • EQE light perovskite light-emitting devices
  • PeLED organic light-emitting devices
  • Electrons and holes are injected and transported into the perovskite light-emitting layer (EML) through the electron transport layer (ETL) and hole transport layer (HTL) respectively.
  • Radiation complex luminescence At present, the research direction in the PeLED field is still mainly focused on continuously improving the EQE of the three primary colors R, G, and blue (B) light PeLED devices.
  • the quality and coverage of the perovskite film in the EML layer, the balance of electron and hole injection and transport, and the light extraction rate, etc. all play a decisive role in the emission EQE of the PeLED device.
  • ETL energy level and mobility matching degree among ETL, EML and HTL directly determines the balance of electron and hole injection and transport.
  • the injection and transport rate of ETL will be better than that of HTL, resulting in an imbalance in the injection and transport of electrons and holes. Improving the balance of ETL and HTL injection and transport will help improve the EQE of PeLED.
  • the commonly used ETL material is TPBi
  • the HTL material is PEDOT:PSS (Al 4083).
  • An object of the present invention is to provide a perovskite-type electroluminescence device, which can solve the problem of imbalance in injection and transport of electrons and holes in the prior art perovskite light-emitting device.
  • the present invention provides a perovskite-type electroluminescent device, comprising a hole transport layer and a light emitting layer arranged on the hole transport layer in sequence; the hole transport layer includes an upper layer The hole transport layer and the lower hole transport layer, wherein the lower hole transport layer is a porous structure layer.
  • the upper hole transport layer adopts the material of the traditional hole transport layer, and the hole transport layer composed of it and the porous structure layer has a high specific surface area, which can effectively increase the hole transport layer and the hole transport layer.
  • the interface contact area of the light-emitting layer improves the injection and transport probability of holes, helps balance the injection and transport of electrons and holes, and further improves the external quantum conversion efficiency of the perovskite light-emitting device.
  • it further includes an anode layer provided under the lower hole transport layer, an electron transport layer provided on the light-emitting layer, and a cathode layer provided on the electron transport layer.
  • the material used for the porous structure layer of the lower hole transport layer is an organic polymer or an inorganic material.
  • the inorganic material is one of molybdenum oxide, aluminum oxide, or nickel oxide.
  • the material used for the upper hole transport layer is polystyrene sulfonic acid or vanadium oxide.
  • the light-emitting layer is a light-emitting material having a perovskite structure.
  • the anode layer includes an electrode having conductivity to transport holes to the hole transport layer
  • the cathode layer includes an electrode having conductivity to transport electrons to the electron transport layer. electrode.
  • Another object of the present invention is to provide a method for preparing a perovskite-type electroluminescent device, which includes the following steps:
  • Step S1 preparing an anode layer
  • Step S2 preparing a lower hole transport layer, the lower hole transport layer being a porous structure layer;
  • Step S3 preparing an upper hole transport layer on the lower hole transport layer
  • Step S4 preparing the light emitting layer, the electron transport layer and the cathode layer.
  • the method for preparing the lower hole transport layer includes a spin coating method, an etching method or a printing method.
  • the method for preparing the upper hole transport layer includes a spin coating method, an evaporation method or a sputtering method.
  • the lower hole transport layer is annealed first, and then the upper hole transport layer is prepared.
  • the beneficial effect of the present invention is that the present invention provides a perovskite-type electroluminescent device, and a composite hole transport layer composed of a porous structure layer and a traditional hole transport layer has a high specific surface area, It can effectively increase the interface contact area with the perovskite light-emitting layer, thereby increasing the probability of hole injection and transportation, helping to balance the injection and transportation of electrons and holes, thereby improving the external quantum conversion efficiency of the perovskite light-emitting device .
  • FIG. 1 is a schematic cross-sectional view of a perovskite-type electroluminescent device provided by Embodiment 1 of the present invention
  • FIG. 2 is a flowchart of a method for preparing a perovskite-type electroluminescent device provided in Example 2 of the present invention.
  • FIG. 1 shows a schematic cross-sectional view of the perovskite-type electroluminescent device provided in this embodiment, including anode layers 1 arranged in sequence. , Hole transport layer 2, light emitting layer 3, electron transport layer 4 and cathode layer 5.
  • the hole transport layer 2 is provided on the anode layer 1
  • the light emitting layer 3 is provided on the hole transport layer 2
  • the electron transport layer 4 is provided on the light emitting layer 3
  • the cathode layer 5 is provided on the electron transport layer 4.
  • the anode layer 5 may specifically be indium tin oxide (ITO, Indium Tin Oxides) or indium zinc oxide (IZO, Idium Zinc Oxides) or indium gallium zinc oxide (IGZO, Indium Gallium Zinc Oxides), etc., are not limited here.
  • ITO Indium Tin Oxides
  • IZO indium zinc oxide
  • IGZO indium gallium zinc oxide
  • the light-emitting layer 3 is a light-emitting material with a perovskite structure, the perovskite material is an organic hybrid ABX3 cubic crystal structure, A is an organic amine group; B is a fourth main group metal or transition metal; X is a monohalide group A combination of elements or polyhalogen elements.
  • the anode layer 1 includes an electrode having conductivity to transport holes to the hole transport layer 2
  • the cathode layer 5 includes an electrode having conductivity to transport electrons to the electron transport layer 4.
  • the hole transport layer 2 includes a lower hole transport layer 21 and an upper hole transport layer 22 provided on the lower hole transport layer 21.
  • the lower hole transport layer 21 is a porous structure layer
  • the upper hole transport layer 22 uses the material of the traditional hole transport layer
  • the hole transport layer 2 composed of the upper hole transport layer 22 and the lower hole transport layer 21 has a high
  • the specific surface area can effectively increase the interface contact area between the hole transport layer 2 and the light emitting layer 3, thereby increasing the probability of injection and transport of holes, helping to balance the injection and transport of electrons and holes, thereby improving the performance of the perovskite light-emitting device. External quantum conversion efficiency.
  • the material of the porous structure layer is an organic polymer or an inorganic material.
  • the inorganic material can be molybdenum oxide, aluminum oxide or nickel oxide, which can be determined as required and is not limited herein.
  • the material of the upper hole transport layer 22 can be polystyrene sulfonic acid or vanadium oxide.
  • This embodiment provides a method for preparing the perovskite type electroluminescent device described in Example 1. Please refer to FIG. 2.
  • FIG. 2 shows the method for preparing the perovskite type electroluminescent device provided in this embodiment.
  • the flowchart includes the following steps:
  • Step S1 preparing an anode layer
  • Step S2 preparing a lower hole transport layer, and the lower hole transport layer is a porous structure layer;
  • the method of preparing the lower hole transport layer includes spin coating, etching, or printing.
  • Step S3 preparing an upper hole transport layer on the lower hole transport layer
  • the lower hole transport layer is annealed first, and then the upper hole transport layer is prepared.
  • the method for preparing the upper hole transport layer includes spin coating, evaporation or sputtering.
  • Step S4 preparing the light emitting layer, the electron transport layer and the cathode layer.
  • the beneficial effect of the present invention is that the present invention provides a perovskite-type electroluminescent device, and a composite hole transport layer composed of a porous structure layer and a traditional hole transport layer has a high specific surface area, It can effectively increase the interface contact area with the perovskite light-emitting layer, thereby increasing the probability of hole injection and transportation, helping to balance the injection and transportation of electrons and holes, thereby improving the external quantum conversion efficiency of the perovskite light-emitting device .

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明提供一种钙钛矿型电致发光器件及其制备方法，钙钛矿型电致发光器件包括依次设置的空穴传输层和设置在所述空穴传输层上的发光层；所述空穴传输层包括上层空穴传输层和下层空穴传输层，其中所述下层空穴传输层为多孔结构层。其中所述上层空穴传输层采用传统空穴传输层的材料，其与所述多孔结构层组成的所述空穴传输层具备高的比表面积，可有效增大所述空穴传输层与所述发光层的界面接触面积，从而提升空穴的注入传输机率，有助于电子与空穴的注入输运平衡，进而提高钙钛矿发光器件的外量子转换效率。

Description

一种钙钛矿型电致发光器件及其制备方法 技术领域
本发明涉及显示面板技术领域，特别涉及一种钙钛矿型电致发光器件及其制备方法。
 背景技术
钙钛矿材料（ABX3）具有光电性能优异，带隙可调，可溶液制备，成本低廉等特点，其中，A为甲胺（MA+），甲脒（FA+），铯（Cs+）或有机大分子等，B为铅（Pb2+），锡（Sn2+）等，X为卤素氯（Cl-），溴（Br-），碘（I-）等。目前，钙钛矿材料在太阳能电池领域中的光电转换效率已达到23.7%，超过传统硅基太阳能电池，同时其稳定性问题也正逐步得到解决，具备可观的商用前景。
而钙钛矿材料应用于显示领域（PeLED）的步伐也紧随其后，经过短短四年的发展，基于红（R）和绿（G）光钙钛矿发光器件的外量子转换效率（EQE）均达到20%以上，具备可实现高色纯，广色域及低成本显示的巨大潜力。
PeLED的器件结构及工作原理与有机发光器件（OLED）相似，电子与空穴分别通过电子传输层（ETL）及空穴传输层（HTL）注入传输至钙钛矿发光层（EML）中，实现辐射复合发光。目前PeLED领域的研究方向仍主要集中在不断提升三原色R、G、蓝（B）光PeLED器件的EQE。其中，EML层钙钛矿薄膜质量及覆盖度，电子与空穴注入输运的平衡程度及光抽取率等，均对PeLED器件发光EQE起着决定性作用。而ETL，EML及HTL三者之间的能级及迁移率匹配度直接决定电子与空穴注入输运的平衡程度。通常来说，ETL的注入输运速率会优于HTL，造成电子与空穴注入输运不平衡，提高ETL和HTL注入输运的平衡有助于提高PeLED的EQE。目前，常用的ETL材料为TPBi，HTL材料为PEDOT:PSS (Al 4083)。
因此，确有必要来开发一种新型的钙钛矿型电致发光器件，以克服现有技术的缺陷。
 技术问题
本发明的一个目的是提供一种钙钛矿型电致发光器件，其能够解决现有技术钙钛矿发光器件中的电子与空穴注入输运不平衡的问题。
 技术解决方案
为实现上述目的，本发明提供一种钙钛矿型电致发光器件，包括依次设置的空穴传输层和设置在所述空穴传输层上的发光层；所述空穴传输层包括上层空穴传输层和下层空穴传输层，其中所述下层空穴传输层为多孔结构层。
其中所述上层空穴传输层采用传统空穴传输层的材料，其与所述多孔结构层组成的所述空穴传输层具备高的比表面积，可有效增大所述空穴传输层与所述发光层的界面接触面积，从而提升空穴的注入传输机率，有助于电子与空穴的注入输运平衡，进而提高钙钛矿发光器件的外量子转换效率。
进一步的，在其他实施方式中，其还包括设置在所述下层空穴传输层下的阳极层、设置在所述发光层上的电子传输层和设置在所述电子传输层上的阴极层。
进一步的，在其他实施方式中，其中所述下层空穴传输层的多孔结构层采用的材料为有机聚合物或无机材料。
进一步的，在其他实施方式中，其中所述无机材料为钼氧化物、铝氧化物或镍氧化物中的一种。
进一步的，在其他实施方式中，其中所述上层空穴传输层采用的材料为聚苯乙烯磺酸或钒氧化物。
进一步的，在其他实施方式中，其中所述发光层为具有钙钛矿结构的发光材料。
进一步的，在其他实施方式中，其中所述阳极层包含具有导电性以输送空穴到所述空穴传输层的电极，所述阴极层包含具有导电性以输送电子到所述电子传输层的电极。
本发明的又一目的是提供一种钙钛矿型电致发光器件的制备方法，包括以下步骤：
步骤S1：制备阳极层；
步骤S2：制备下层空穴传输层，所述下层空穴传输层为多孔结构层；
步骤S3：在所述下层空穴传输层上制备上层空穴传输层；
步骤S4：制备发光层、电子传输层和阴极层。
进一步的，在其他实施方式中，其中所述步骤S2中，制备所述下层空穴传输层的方法包括旋涂法、刻蚀法或印刷法。
进一步的，在其他实施方式中，其中所述步骤S3中，制备所述上层空穴传输层的方法包括旋涂法、蒸镀法或溅射法。
进一步的，在其他实施方式中，其中所述步骤S3中，其为先对所述下层空穴传输层进行退火处理，然后再制备所述上层空穴传输层。
 有益效果
相对于现有技术，本发明的有益效果在于：本发明提供一种钙钛矿型电致发光器件，由多孔结构层和传统空穴传输层组成的复合空穴传输层具备高的比表面积，可有效增大其与钙钛矿发光层的界面接触面积，从而提升空穴的注入传输机率，有助于电子与空穴的注入输运平衡，进而提高钙钛矿发光器件的外量子转换效率。
 附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例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发明的一些实施例，对于本领域技术人员来讲，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他的附图。
图1为本发明实施例1提供的钙钛矿型电致发光器件的剖视示意图；
图2为本发明实施例2提供的钙钛矿型电致发光器件的制备方法的流程图。
 本发明的最佳实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
这里所公开的具体结构和功能细节仅仅是代表性的，并且是用于描述本发明的示例性实施例的目的。但是本发明可以通过许多替换形式来具体实现，并且不应当被解释成仅仅受限于这里所阐述的实施例。
在本发明的描述中，需要理解的是，术语“中心”、“横向”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
实施例1
本实施例提供一种钙钛矿型电致发光器件，请参阅图1，图1所示为本实施例提供的钙钛矿型电致发光器件的剖视示意图，包括依次设置的阳极层1、空穴传输层2、发光层3、电子传输层4和阴极层5。空穴传输层2设置于阳极层1上，发光层3设置于空穴传输层2上，电子传输层4设置于发光层3上，阴极层5设置于电子传输层4上。
在具体实施时，阳极层5具体可以采用氧化铟锡 (ITO,Indium Tin  Oxides)或氧化铟锌(IZO,Idium Zinc Oxides)或氧化铟镓锌(IGZO,Indium Gallium Zinc Oxides) 等制作，在此不做限定。
发光层3为具有钙钛矿结构的发光材料，钙钛矿材料为有机杂化ABX3型立方晶系结构，A为有机胺集团；B为第四主族金属或过渡金属；X为一元卤族元素或多元卤族元素的组合。
阳极层1包含具有导电性以输送空穴到空穴传输层2的电极，阴极层5包含具有导电性以输送电子到电子传输层4的电极。
空穴传输层2包括下层空穴传输层21和设置在下层空穴传输层21上的上层空穴传输层22。其中下层空穴传输层21为多孔结构层，上层空穴传输层22采用传统空穴传输层的材料，上层空穴传输层22和下层空穴传输层21组成的空穴传输层2具备高的比表面积，可有效增大空穴传输层2与发光层3的界面接触面积，从而提升空穴的注入传输机率，有助于电子与空穴的注入输运平衡，进而提高钙钛矿发光器件的外量子转换效率。
在本实施例中，多孔结构层的材料采用有机聚合物或无机材料，无机材料可以采用钼氧化物，也可以采用铝氧化物或镍氧化物，可随需要而定，在此不做限定。
在本实施例中，上层空穴传输层22的材料可以采用聚苯乙烯磺酸，也可以采用钒氧化物。
实施例2
本实施例提供一种实施例1所述的钙钛矿型电致发光器件的制备方法，请参阅图2，图2所示为本实施例提供的钙钛矿型电致发光器件的制备方法的流程图，包括以下步骤：
步骤S1：制备阳极层；
步骤S2：制备下层空穴传输层，下层空穴传输层为多孔结构层；
制备下层空穴传输层的方法包括旋涂法、刻蚀法或印刷法。
步骤S3：在下层空穴传输层上制备上层空穴传输层；
其中先对下层空穴传输层进行退火处理，然后再制备上层空穴传输层，制备上层空穴传输层的方法包括旋涂法、蒸镀法或溅射法。
步骤S4：制备发光层、电子传输层和阴极层。
相对于现有技术，本发明的有益效果在于：本发明提供一种钙钛矿型电致发光器件，由多孔结构层和传统空穴传输层组成的复合空穴传输层具备高的比表面积，可有效增大其与钙钛矿发光层的界面接触面积，从而提升空穴的注入传输机率，有助于电子与空穴的注入输运平衡，进而提高钙钛矿发光器件的外量子转换效率。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (13)

  1. 一种钙钛矿型电致发光器件，包括依次设置的空穴传输层和设置在所述空穴传输层上的发光层；其中，所述空穴传输层包括上层空穴传输层和下层空穴传输层，其中所述下层空穴传输层为多孔结构层。
  2. 根据权利要求1所述的钙钛矿型电致发光器件，其中，其还包括设置在所述下层空穴传输层下的阳极层、设置在所述发光层上的电子传输层和设置在所述电子传输层上的阴极层。
  3. 根据权利要求1所述的钙钛矿型电致发光器件，其中，所述下层空穴传输层的多孔结构层采用的材料为有机聚合物或无机材料。
  4. 根据权利要求3所述的钙钛矿型电致发光器件，其中，所述无机材料为钼氧化物、铝氧化物或镍氧化物中的一种。
  5. 根据权利要求1所述的钙钛矿型电致发光器件，其中，所述上层空穴传输层采用的材料为聚苯乙烯磺酸或钒氧化物。
  6. 根据权利要求2所述的钙钛矿型电致发光器件，其中，所述阳极层包含具有导电性以输送空穴到所述空穴传输层的电极，所述阴极层包含具有导电性以输送电子到所述电子传输层的电极。
  7. 权利要求1所述的钙钛矿型电致发光器件的制备方法，其中，包括以下步骤：
    步骤S1：制备阳极层；
    步骤S2：制备下层空穴传输层，所述下层空穴传输层为多孔结构层；
    步骤S3：在所述下层空穴传输层上制备上层空穴传输层；
    步骤S4：制备发光层、电子传输层和阴极层。
  8. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其特征在于，所述步骤S2中，制备所述下层空穴传输层的方法包括旋涂法、刻蚀法或印刷法。
  9. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其中，所述步骤S3中，制备所述上层空穴传输层的方法包括旋涂法、蒸镀法或溅射法。
  10. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其中，所述步骤S3中，其为先对所述下层空穴传输层进行退火处理，然后再制备所述上层空穴传输层。
  11. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其中，所述下层空穴传输层的多孔结构层采用的材料为有机聚合物或无机材料。
  12. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其中，所述无机材料为钼氧化物、铝氧化物或镍氧化物中的一种。
  13. 根据权利要求7所述的钙钛矿型电致发光器件的制备方法，其中，所述上层空穴传输层采用的材料为聚苯乙烯磺酸或钒氧化物。
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