WO2021114387A1 - 钙钛矿发光器件及其制备方法、显示器 - Google Patents

钙钛矿发光器件及其制备方法、显示器 Download PDF

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WO2021114387A1
WO2021114387A1 PCT/CN2019/127704 CN2019127704W WO2021114387A1 WO 2021114387 A1 WO2021114387 A1 WO 2021114387A1 CN 2019127704 W CN2019127704 W CN 2019127704W WO 2021114387 A1 WO2021114387 A1 WO 2021114387A1
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Prior art keywords
layer
light
injection
emitting
transport
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English (en)
French (fr)
Inventor
段淼
李佳育
徐君哲
尹勇明
吴永伟
江沛
何波
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Priority to US16/759,477 priority Critical patent/US11302886B2/en
Publication of WO2021114387A1 publication Critical patent/WO2021114387A1/zh
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    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • H10K85/30—Coordination compounds
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3031—Two-side emission, e.g. transparent OLEDs [TOLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—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]
    • H10K50/17—Carrier injection 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • 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

  • This application relates to the field of display technology, in particular to a perovskite light-emitting device, a preparation method thereof, and a display.
  • Light-emitting diodes are currently the most popular materials and technologies in the field of light-emitting and display. With the advancement of science and technology, transparent display technology has become the development trend of future display, so there is a higher demand for performance parameters such as color purity, brightness, and luminous efficiency of light-emitting diodes.
  • Organic light-emitting diodes are the most mentioned in the current transparent display technology category.
  • the transparent display technology based on organic light-emitting diodes has developed rapidly and has become a research hotspot.
  • organic light-emitting diodes use organic materials, so the color purity is not high, and their pure colors require color filters to produce.
  • This application provides a perovskite light-emitting device, a preparation method thereof, and a display, so as to solve the problem of low color purity of organic light-emitting diodes in the prior art.
  • a technical solution adopted in this application is to provide a perovskite light-emitting device, which includes a first injection layer, a first transmission layer, a light-emitting layer, and a second layer that are stacked in sequence.
  • the first injection layer includes indium tin oxide
  • the second injection layer includes carbon nanotubes
  • the light emitting layer includes halide perovskite.
  • the light emitted from the light emitting layer is simultaneously emitted from the first injection layer and the second injection layer.
  • the injection layer is ejected.
  • Another technical solution adopted in this application is to provide a method for preparing a perovskite light-emitting device.
  • the method includes laying indium tin oxide on a substrate by magnetron sputtering to obtain a first injection layer.
  • another technical solution adopted in this application is to provide a display including the above-mentioned perovskite light-emitting device.
  • this application uses transparent and conductive indium tin oxide as the first injection layer, and uses carbon nanotubes as the second injection layer.
  • the carbon nanotubes themselves have good conductivity and stability.
  • a conductive grid structure is formed.
  • different carbon nanotubes are staggered and overlapped, so that electrons can not only be transported along the carbon nanotube's own direction, but also can be transported to other carbon nanotubes through contact sites, so that the movement of electrons runs through the entire carbon.
  • the nanotube grid in order to achieve good electrical conductivity of the electrode, and the holes between different carbon nanotubes can let light pass through, so as to realize the light transmission function.
  • the halide perovskite is used as the light-emitting layer, and the halide perovskite material has the properties of high fluorescence quantum efficiency, adjustable optical band gap, and high color purity, so that the produced light-emitting layer has excellent purity and high purity.
  • the light emitted by the light emitting layer is simultaneously emitted from the first injection layer and the second injection layer, thereby realizing the effect of double-sided light emission.
  • Fig. 1 is a schematic cross-sectional view of an embodiment of a perovskite light-emitting device provided by the present application;
  • Fig. 2 is a schematic diagram of an embodiment of a carbon nanotube conductive grid provided by the present application
  • FIG. 3 is a schematic flowchart of an embodiment of a method for manufacturing a perovskite light-emitting device provided by the present application
  • FIG. 4 is a schematic flowchart of an embodiment of a method for manufacturing a perovskite light-emitting device provided by the present application
  • FIG. 5 is a schematic structural diagram of an embodiment of the display provided by the present application.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a perovskite light-emitting device 100 provided by the present application
  • FIG. 2 is a schematic view of an embodiment of a carbon nanotube conductive grid provided by the present application.
  • the present application provides a perovskite light-emitting device 100, and the perovskite light-emitting device 100 of the present application is an inorganic light-emitting LED device.
  • the perovskite light-emitting device 100 includes a first injection layer 10, a first transmission layer 20, a light-emitting layer 30, a second transmission layer 40, and a second injection layer 50 that are sequentially stacked.
  • the first injection layer 10 includes indium tin oxide.
  • the second injection layer 50 includes carbon nanotubes, and the light-emitting layer 30 includes halide perovskite.
  • ITO Indium tin oxide
  • ITO Indium tin oxide
  • tin oxide is a mixture of indium oxide and tin oxide, usually in a mass ratio of 90% indium oxide and 10% tin oxide.
  • Indium tin oxide has the characteristics of transparency and conductivity in the form of a film.
  • the nano-silver wires are easily oxidized at high temperature and affect the conductivity of the nano-silver wires.
  • the nano-silver wire will slowly penetrate into the light-emitting layer 30 made of halide perovskite and chemically react with it, corroding the halide perovskite and causing the perovskite light-emitting device 100 to fail.
  • carbon nanotubes themselves have good conductivity and stability, and carbon nanotubes are resistant to high temperature and are not easily oxidized. They are suitable for various later baking processes and are therefore more suitable for industrial production.
  • a conductive grid structure is formed (as shown in FIG. 2).
  • different carbon nanotubes are staggered and overlapped, so that electrons can not only be transported along the carbon nanotube's own direction, but also can be transported to other carbon nanotubes through contact sites, so that the movement of electrons runs through the entire carbon.
  • the holes between different carbon nanotubes can let light pass through, so as to realize the light transmission function.
  • the transparency of carbon nanotubes can be adjusted by changing the number of carbon nanotubes and the thickness of the film.
  • the halide perovskite material has properties such as high fluorescence quantum efficiency, adjustable optical band gap, and high color purity.
  • the halide perovskite film can be prepared by a low-cost solution method, so the manufacturing cost of the light-emitting device can be greatly reduced.
  • the researchers of the present application found in experiments that the external quantum efficiency of the green light and red light perovskite light-emitting diodes successively exceeded 20%, so that the halide perovskite as the light-emitting layer 30 becomes possible.
  • the light emitted from the light emitting layer 30 is simultaneously emitted from the first injection layer 10 and the second injection layer 50, thereby achieving the effect of double-sided light emission.
  • the perovskite light-emitting device 100 with double-sided light-emitting effect will be widely used in the fields of commercial display, advertising window, car glass, and city decoration.
  • the first injection layer 10 can be used to receive injection of electrons, the first transport layer 20 is used to transport electrons to the light-emitting layer 30, the second injection layer 50 is used to receive hole injection, and the second transport layer 40 is used to The holes are transported to the light-emitting layer 30. Since the work function of indium tin oxide is lower than that of carbon nanotubes, it will be easier for electrons to be injected from the first injection layer 10, which will be beneficial to the improvement of the properties of the perovskite light-emitting device 100.
  • the working principle of the perovskite light-emitting device 100 can be simply divided into the following processes:
  • the injected electrons migrate from the first transport layer 20 to the light emitting layer 30, and the injected holes migrate from the second transport layer 40 to the light emitting layer 30;
  • the excitons continuously diffuse freely in the halide perovskite film, and are deactivated by radiation or non-radiation;
  • the first injection layer 10 also includes an aliphatic amine disposed on the indium tin oxide, and the aliphatic amine is used to modify the indium tin oxide to reduce the work function of the indium tin oxide. Electrons are injected from the first injection layer 10. The lower the barrier of the first injection layer 10, the faster the injection of electrons. The surface modification of indium tin oxide with fatty amine molecules reduces the work function of indium tin oxide. The role of the work function is to lower the barrier of the first injection layer 10.
  • the first transport layer 20 includes tin dioxide, and the tin dioxide is used to transport electrons to the light-emitting layer 30.
  • Tin dioxide is a metal inorganic oxide.
  • the thermal decomposition temperature of tin dioxide is much higher than that of organics, and its chemical stability is much better. Therefore, the first transmission layer 20 made of tin dioxide is beneficial to the stability of the perovskite light-emitting device 100 Sex.
  • the second transport layer 40 includes polymethyl methacrylate, and the polymethyl methacrylate is used to transport holes to the light emitting layer 30. Because the transmission rate of electrons in the first transport layer 20 is faster than the transmission rate of holes in the second transport layer 40, this will cause the electrons to be injected into the light-emitting layer 30 first, and the injection of holes will be slower, resulting in electron-vacancy. The imbalance of holes, so if polymethyl methacrylate (PTAA) with high mobility is selected as the hole transport layer, it will facilitate the transport of holes, and thus play a beneficial role in the balance of electron-hole injection.
  • PTAA polymethyl methacrylate
  • FIG. 3 is a schematic flowchart of an embodiment of a method for manufacturing the perovskite light-emitting device 100 provided in the present application.
  • PET polyethylene terephthalate
  • glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Indium tin oxide is laid on the substrate by magnetron sputtering to prepare the transparent first injection layer 10.
  • the first injection layer 10 may be used to receive injection of electrons.
  • the tin dioxide solution is spin-coated on the first injection layer 10, the rotation speed can be 2000 r/min, and the rotation time can be 50 seconds, and the substrate is transferred to a hot stage for annealing treatment to obtain the first transfer layer 20.
  • the first transport layer 20 is used to transport electrons to the light emitting layer 30.
  • S103 Disposing the halide perovskite on the first transmission layer 20 by spin coating to obtain the light emitting layer 30.
  • the rotation speed can be 4000r/min
  • the rotation time can be 30 seconds
  • the anti-solvent chlorobenzene is added dropwise to the first transmission layer 20 for extraction to make the halide calcium
  • the titanium ore is rapidly precipitated to form a film, and the substrate is transferred to a hot stage for annealing treatment to obtain the light-emitting layer 30.
  • the light-emitting layer 30 obtained by this method is of high quality, and the light-emitting layer 30 is flat and dense in quality.
  • a second transmission layer 40 is provided on the light-emitting layer 30.
  • the polymethyl methacrylate solution is spin-coated on the light-emitting layer 30 at a rotation speed of 3000 r/min, and the substrate is transferred to a hot stage for annealing treatment to obtain the second transmission layer 40.
  • the second transport layer 40 is used to transport holes to the light-emitting layer 30.
  • the carbon nanotube ink is dropped on the second transfer layer 40 and then spin-coated or knife-coated to form a film, and dried to obtain the second injection layer 50.
  • the second injection layer 50 is used to receive injection of holes.
  • the manufacturing of the perovskite light-emitting device 100 is completed through step S101 to step S105.
  • FIG. 4 is a schematic flowchart of an embodiment of a method for manufacturing the perovskite light-emitting device 100 provided in the present application.
  • PET polyethylene terephthalate
  • glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • Optical substrate The polyethylene terephthalate (PET) or glass is ultrasonically cleaned with a 1:1 mixture of deionized water and alcohol, and baked in a drying oven for 2 hours to obtain a clean, transparent glass.
  • aliphatic amine can be continued to be laid on the indium tin oxide to prepare a transparent first injection layer 10.
  • the first injection layer 10 may be used to receive injection of electrons.
  • Aliphatic amines are used to modify indium tin oxide to reduce the work function of indium tin oxide. Electrons are injected from the first injection layer 10. The lower the barrier of the first injection layer 10, the faster the injection of electrons. The surface modification of indium tin oxide with fatty amine molecules reduces the work function of indium tin oxide. The role of the work function is to lower the barrier of the first injection layer 10.
  • the tin dioxide solution is spin-coated on the first injection layer 10, the rotation speed can be 2000 r/min, and the rotation time can be 50 seconds, and the substrate is transferred to a hot stage for annealing treatment to obtain the first transfer layer 20.
  • the first transport layer 20 is used to transport electrons to the light emitting layer 30.
  • S204 Disposing the halide perovskite on the first transmission layer 20 by spin coating to obtain the light emitting layer 30.
  • the rotation speed can be 4000r/min
  • the rotation time can be 30 seconds
  • the anti-solvent chlorobenzene is added dropwise to the first transmission layer 20 for extraction to make the halide calcium
  • the titanium ore is rapidly precipitated to form a film, and the substrate is transferred to a hot stage for annealing treatment to obtain the light-emitting layer 30.
  • the light-emitting layer 30 obtained by this method is of high quality, and the light-emitting layer 30 is flat and dense in quality.
  • a second transmission layer 40 is provided on the light-emitting layer 30.
  • the polymethyl methacrylate solution is spin-coated on the light-emitting layer 30 at a rotation speed of 3000 r/min, and the substrate is transferred to a hot stage for annealing treatment to obtain the second transmission layer 40.
  • the second transport layer 40 is used to transport holes to the light-emitting layer 30.
  • the carbon nanotube ink is dropped on the second transfer layer 40 and then spin-coated or knife-coated to form a film, and dried to obtain the second injection layer 50.
  • the second injection layer 50 is used to receive injection of holes.
  • the manufacturing of the perovskite light-emitting device 100 is completed through step S101 to step S105.
  • FIG. 5 is a schematic structural diagram of an embodiment of a display 1000 provided by the present application.
  • the display 1000 of the present application includes the perovskite light-emitting device 100 in the above-mentioned embodiment and a face frame 200 sleeved around the perovskite light-emitting device 100.
  • the perovskite light-emitting device 100 can display on both sides.

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Abstract

一种钙钛矿发光器件及其制备方法、显示器，该钙钛矿发光器件（100）包括依次层叠设置的第一注入层（10）、第一传输层（20）、发光层（30）、第二传输层（40）和第二注入层（50），第一注入层（10）包括氧化铟锡，第二注入层（50）包括碳纳米管，发光层（30）包括卤化物钙钛矿，其中，发光层（30）的出光同时从第一注入层（10）和第二注入层（50）射出。该钙钛矿发光器件（100）能够稳定地双面出光。

Description

钙钛矿发光器件及其制备方法、显示器 技术领域
本申请涉及显示技术领域，特别是涉及钙钛矿发光器件及其制备方法、显示器。
 背景技术
发光二极管是当前发光与显示领域最热门的材料与技术。随着科技的进步，透明显示技术成为未来显示的发展趋势，因此对发光二极管的色纯度、亮度、发光效率等性能参数有更高的需求。
 技术问题
在目前透明显示技术范畴内被提及最多的当属有机发光二极管，基于有机发光二极管的透明显示技术发展十分迅速，成为研究的热点。但有机发光二极管使用的是有机材料，因此色纯度不高，其纯色需要彩色过滤器才能产生。
因此，制备出色纯度高的透明发光二极管是目前面临的问题。
 技术解决方案
本申请提供了钙钛矿发光器件及其制备方法、显示器，以解决现有技术中有机发光二极管色纯度不高的问题。
为解决上述技术问题，本申请采用的一个技术方案是：提供一种钙钛矿发光器件，该钙钛矿发光器件包括依次层叠设置的第一注入层、第一传输层、发光层、第二传输层和第二注入层，第一注入层包括氧化铟锡，第二注入层包括碳纳米管，发光层包括卤化物钙钛矿，其中，发光层的出光同时从第一注入层和第二注入层射出。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种钙钛矿发光器件的制备方法，该制备方法包括通过磁控溅射在基板上铺设氧化铟锡以得到第一注入层；在第一注入层上设置第一传输层；通过旋涂的方式将卤化物钙钛矿设置在第一传输层以得到发光层；在发光层上设置第二传输层；将碳纳米管油墨滴在第二传输层上形成第二注入层，从而得到钙钛矿发光器件，其中，发光层的出光同时从第一注入层和第二注入层射出。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种显示器，该显示器包括上述的钙钛矿发光器件。
 有益效果
本申请的有益效果为：本申请用具有透明和导电的特性的氧化铟锡作为第一注入层，用碳纳米管作为第二注入层，碳纳米管本身具有很好的导电性和稳定性，把碳纳米管涂布于第二传输层上时，会形成导电网格结构。其中，不同的碳纳米管相交错搭接，使得电子不仅能够沿着碳纳米管自身方向输运，而且可以通过接触位点传输到其他的碳纳米管上，进而使得电子的运动贯穿于整个碳纳米管网格中，以实现电极良好的导电性，而不同碳纳米管之间的孔洞则可以让光通过，从而实现透光功能。另外，以卤化物钙钛矿作为发光层，卤化物钙钛矿材料具有较高的荧光量子效率、光学带隙可调、色彩纯度高等性质，这样制作出来的发光层出色纯度高。发光层的出光同时从第一注入层和第二注入层射出，从而实现双面发光的效果。
 附图说明
图1是本申请提供的钙钛矿发光器件的一实施例的截面示意图；
图2是本申请提供的碳纳米管导电网格的一实施例的示意图；
图3是本申请提供的钙钛矿发光器件的制备方法的一实施例的流程示意图；
图4是本申请提供的钙钛矿发光器件的制备方法的一实施例的流程示意图；
图5是本申请提供的显示器的一实施例的结构示意图。
 本发明的实施方式
下面将对本申请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申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，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，都属于本申请保护的范围。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
请参阅图1和图2，图1是本申请提供的钙钛矿发光器件100的一实施例的截面示意图，图2是本申请提供的碳纳米管导电网格的一实施例的示意图。
本申请提供了一种钙钛矿发光器件100，本申请钙钛矿发光器件100为无机发光LED器件。
钙钛矿发光器件100包括依次层叠设置的第一注入层10、第一传输层20、发光层30、第二传输层40和第二注入层50，第一注入层10包括氧化铟锡，第二注入层50包括碳纳米管，发光层30包括卤化物钙钛矿。
氧化铟锡(ITO)是一种铟氧化物和锡氧化物的混合物，通常质量比为90%铟氧化物和10%锡氧化物。氧化铟锡在薄膜状时具有透明和导电的特性。
在本申请研发人员的前期研发中发现，具有透光性质的第二注入层50用纳米银线来制作时，纳米银线在高温状态下容易被氧化而影响纳米银线的导电性，另外，纳米银线会慢慢渗透到用卤化物钙钛矿制作的发光层30并与之发生化学反应，腐蚀卤化物钙钛矿进而导致钙钛矿发光器件100失效。
从而研发人员通过实验众多材料后发现，碳纳米管本身具有很好的导电性和稳定性，碳纳米管耐高温不易被氧化，适合后期的各种烘烤制程，因此更加适合工业化生产。把碳纳米管涂布于第二传输层40上时，会形成导电网格结构（如图2所示）。其中，不同的碳纳米管相交错搭接，使得电子不仅能够沿着碳纳米管自身方向输运，而且可以通过接触位点传输到其他的碳纳米管上，进而使得电子的运动贯穿于整个碳纳米管网格中，以实现电极良好的导电性，而不同碳纳米管之间的孔洞则可以让光通过，从而实现透光功能。另外，碳纳米管的透明度可以通过改变碳纳米管的数量和薄膜的厚度来调节。
本申请的研发人员在实验中发现卤化物钙钛矿材料具有较高的荧光量子效率、光学带隙可调、色彩纯度高等性质。相比于有机发光二极管中需要蒸镀成膜的有机分子发光层30而言，卤化物钙钛矿薄膜可采用低成本的溶液法制备，因此可以大大降低发光器件的制作成本。另外，本申请的研发人员在实验中发现绿光和红光钙钛矿发光二极管的外量子效率接连突破20%，以使卤化物钙钛矿作为发光层30成为可能性。
发光层30的出光同时从第一注入层10和第二注入层50射出，从而实现双面发光的效果。具有双面发光效果的钙钛矿发光器件100将在商业显示、广告橱窗、车载玻璃和市内装饰等领域得到广泛的应用。
第一注入层10可以用于接收电子的注入，第一传输层20用于将电子传输至发光层30，第二注入层50用于接收空穴的注入，第二传输层40用于将空穴传输至发光层30。由于氧化铟锡的功函数比碳纳米管的功函数低，那么电子从第一注入层10注入将更加容易，这将有利于钙钛矿发光器件100性质的提升。
钙钛矿发光器件100发光的工作原理可简单地分为以下几个过程：
1、在外加电场的作用下，电子从第一注入层10注入，空穴从第二注入层50注入；
2、注入的电子从第一传输层20向发光层30迁移，注入空穴从第二传输层40向发光层30迁移；
3、电子和空穴在发光层30中相遇产生激子；
4、激子在卤化物钙钛矿薄膜中不断地作自由扩散运动，并以辐射或无辐射的方式失活；
5、当激子由激发态以辐射跃迁的方式回到基态，就可以观察到电致发光现象，发射光的颜色由激发态到基态的能级差所决定。
第一注入层10还包括设置在氧化铟锡上的脂肪胺，脂肪胺用于修饰氧化铟锡，以降低氧化铟锡的功函数。电子从第一注入层10注入，第一注入层10的势垒越低将有利于电子更快地注入，采用脂肪胺类分子对氧化铟锡进行表面修饰来降低氧化铟锡功函数，而降低功函数的作用就是降低第一注入层10的势垒。
第一传输层20包括二氧化锡，二氧化锡用于将电子传输至发光层30。二氧化锡为金属无机氧化物，二氧化锡的热分解温度比有机物高的多，化学稳定性要好很多，因此采用二氧化锡制作的第一传输层20有利于钙钛矿发光器件100的稳定性。
第二传输层40包括聚甲基丙烯酸甲酯，聚甲基丙烯酸甲酯用于将空穴传输至发光层30。因为电子在第一传输层20中的传输速率要比空穴在第二传输层40中的传输速率快，这样会导致电子先注入发光层30，空穴则注入较慢，而造成电子-空穴的不平衡，所以如果选用高迁移率的聚甲基丙烯酸甲酯（PTAA）作为空穴传输层，将有利于空穴的传输，从而对电子-空穴的注入平衡起到有利作用。
请参阅图1和图3，图3是本申请提供的钙钛矿发光器件100的制备方法的一实施例的流程示意图。
S101：通过磁控溅射在基板上铺设氧化铟锡以得到第一注入层10。
将聚对苯二甲酸乙二醇酯（Polyethylene terephthalate，PET）或者玻璃用去离子水和酒精的1:1混合液超声清洗干净，放入干燥烘箱内烘烤2小时，以得到干净的具有透光性质的基板。
在基板上通过磁控溅射的方式铺设氧化铟锡以制备得到透明的第一注入层10。第一注入层10可以用于接收电子的注入。
S102：在第一注入层10上设置第一传输层20。
在第一注入层10上旋涂二氧化锡溶液，转速可以是2000r/min，转动的时间可以是50秒，将基板转移到热台上退火处理得到第一传输层20。第一传输层20用于将电子传输至发光层30。
S103：通过旋涂的方式将卤化物钙钛矿设置在第一传输层20以得到发光层30。
在第一传输层20上旋涂卤化物钙钛矿溶液，转速可以是4000r/min，转动的时间可以是30秒，向第一传输层20上滴加反溶剂氯苯进行萃取使得卤化物钙钛矿快速析出成膜，将基板转移到热台上退火处理得到发光层30。这种方法得到的发光层30质量很高，发光层30质平整且致密。
S104：在发光层30上设置第二传输层40。
在发光层30上旋涂聚甲基丙烯酸甲酯溶液，转速可以是3000r/min，将基板转移到热台上退火处理得到第二传输层40。第二传输层40用于将空穴传输至发光层30。
S105：将碳纳米管油墨滴在第二传输层40上形成第二注入层50，从而得到钙钛矿发光器件100。
将碳纳米管油墨滴在第二传输层40上后旋涂或刮涂成膜，烘干后得到第二注入层50。第二注入层50用于接收空穴的注入。通过步骤S101至步骤S105完成钙钛矿发光器件100的制作。
本申请中的术语“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。
请参阅图1和图4，图4是本申请提供的钙钛矿发光器件100的制备方法的一实施例的流程示意图。
S201：通过磁控溅射在基板上铺设氧化铟锡。
将聚对苯二甲酸乙二醇酯（Polyethylene terephthalate，PET）或者玻璃用去离子水和酒精的1:1混合液超声清洗干净，放入干燥烘箱内烘烤2小时，以得到干净的具有透光性质的基板。
在基板上通过磁控溅射的方式铺设氧化铟锡。
S202：在氧化铟锡上铺设脂肪胺以得到第一注入层10。
在完成对氧化铟锡铺设后，可以继续在氧化铟锡上铺设脂肪胺，以制备得到透明的第一注入层10。第一注入层10可以用于接收电子的注入。
脂肪胺用于修饰氧化铟锡，以降低氧化铟锡的功函数。电子从第一注入层10注入，第一注入层10的势垒越低将有利于电子更快地注入，采用脂肪胺类分子对氧化铟锡进行表面修饰来降低氧化铟锡功函数，而降低功函数的作用就是降低第一注入层10的势垒。
S203：在第一注入层10上设置第一传输层20。
在第一注入层10上旋涂二氧化锡溶液，转速可以是2000r/min，转动的时间可以是50秒，将基板转移到热台上退火处理得到第一传输层20。第一传输层20用于将电子传输至发光层30。
S204：通过旋涂的方式将卤化物钙钛矿设置在第一传输层20以得到发光层30。
在第一传输层20上旋涂卤化物钙钛矿溶液，转速可以是4000r/min，转动的时间可以是30秒，向第一传输层20上滴加反溶剂氯苯进行萃取使得卤化物钙钛矿快速析出成膜，将基板转移到热台上退火处理得到发光层30。这种方法得到的发光层30质量很高，发光层30质平整且致密。
S205：在发光层30上设置第二传输层40。
在发光层30上旋涂聚甲基丙烯酸甲酯溶液，转速可以是3000r/min，将基板转移到热台上退火处理得到第二传输层40。第二传输层40用于将空穴传输至发光层30。
S206：将碳纳米管油墨滴在第二传输层40上形成第二注入层50，从而得到钙钛矿发光器件100。
将碳纳米管油墨滴在第二传输层40上后旋涂或刮涂成膜，烘干后得到第二注入层50。第二注入层50用于接收空穴的注入。通过步骤S101至步骤S105完成钙钛矿发光器件100的制作。
请参阅图5，图5是本申请提供的显示器1000的一实施例的结构示意图。
本申请的显示器1000包括上述实施例中的钙钛矿发光器件100和套设在钙钛矿发光器件100周边的面框200，钙钛矿发光器件100能够两面进行显示。
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (14)

  1. 一种钙钛矿发光器件，其中，所述钙钛矿发光器件包括依次层叠设置的第一注入层、第一传输层、发光层、第二传输层和第二注入层，所述第一注入层包括氧化铟锡，所述第二注入层包括碳纳米管，所述发光层包括卤化物钙钛矿，其中，所述发光层的出光同时从所述第一注入层和所述第二注入层射出。
  2. 根据权利要求1所述的钙钛矿发光器件，其中，所述第一注入层用于接收电子的注入，所述第一传输层用于将电子传输至所述发光层，所述第二注入层用于接收空穴的注入，所述第二传输层用于将空穴传输至所述发光层。
  3. 根据权利要求2所述的钙钛矿发光器件，其中，所述第一传输层包括二氧化锡，所述二氧化锡用于将电子传输至所述发光层。
  4. 根据权利要求2所述的钙钛矿发光器件，其中，所述第一注入层还包括设置在所述氧化铟锡上的脂肪胺，所述脂肪胺用于修饰所述氧化铟锡，以降低所述氧化铟锡的功函数。
  5. 根据权利要求2所述的钙钛矿发光器件，其中，所述第二传输层包括聚甲基丙烯酸甲酯，所述聚甲基丙烯酸甲酯用于将空穴传输至所述发光层。
  6. 一种钙钛矿发光器件的制备方法，其中，
    通过磁控溅射在基板上铺设氧化铟锡以得到第一注入层；
    在所述第一注入层上设置第一传输层；
    通过旋涂的方式将卤化物钙钛矿设置在所述第一传输层以得到发光层；
    在所述发光层上设置第二传输层；
    将碳纳米管油墨滴在所述第二传输层上形成第二注入层，从而得到所述钙钛矿发光器件，其中，所述发光层的出光同时从所述第一注入层和所述第二注入层射出。
  7. 根据权利要求6所述的制备方法，其中，所述第一注入层用于接收电子的注入，所述第一传输层用于将电子传输至所述发光层，所述第二注入层用于接收空穴的注入，所述第二传输层用于将空穴传输至所述发光层。
  8. 根据权利要求7所述的制备方法，其中，
    所述在所述第一注入层上设置第一传输层的步骤，包括：在所述第一注入层上旋涂二氧化锡溶液；将所述基板转移到热台上退火处理得到第一传输层；
    所述通过旋涂的方式将卤化物钙钛矿设置在所述第一传输层以得到发光层的步骤，包括：在所述第一传输层上旋涂卤化物钙钛矿溶液；向所述第一传输层上滴加反溶剂氯苯；将所述基板转移到热台上退火处理得到发光层；
    所述在所述发光层上设置第二传输层的步骤，包括：在所述发光层上旋涂聚甲基丙烯酸甲酯溶液；将所述基板转移到热台上退火处理得到第二传输层。
  9. 根据权利要求7所述的制备方法，其中，
    所述通过磁控溅射在基板上铺设氧化铟锡以得到第一注入层的步骤，包括：通过磁控溅射在基板上铺设氧化铟锡；在所述氧化铟锡上铺设脂肪胺以得到第一注入层。
  10. 一种显示器，其中，所述显示器包括权利要求1至5任一项所述的钙钛矿发光器件；所述钙钛矿发光器件包括依次层叠设置的第一注入层、第一传输层、发光层、第二传输层和第二注入层，所述第一注入层包括氧化铟锡，所述第二注入层包括碳纳米管，所述发光层包括卤化物钙钛矿，其中，所述发光层的出光同时从所述第一注入层和所述第二注入层射出。
  11. 根据权利要求10所述的显示器，其中，所述第一注入层用于接收电子的注入，所述第一传输层用于将电子传输至所述发光层，所述第二注入层用于接收空穴的注入，所述第二传输层用于将空穴传输至所述发光层。
  12. 根据权利要求11所述的显示器，其中，所述第一传输层包括二氧化锡，所述二氧化锡用于将电子传输至所述发光层。
  13. 根据权利要求11所述的显示器，其中，所述第一注入层还包括设置在所述氧化铟锡上的脂肪胺，所述脂肪胺用于修饰所述氧化铟锡，以降低所述氧化铟锡的功函数。
  14. 根据权利要求11所述的显示器，其中，所述第二传输层包括聚甲基丙烯酸甲酯，所述聚甲基丙烯酸甲酯用于将空穴传输至所述发光层。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150034930A1 (en) * 2012-03-07 2015-02-05 Osram Opto Semiconductors Gmbh Organic light-emitting device
CN105778619A (zh) * 2014-12-17 2016-07-20 中国科学院苏州纳米技术与纳米仿生研究所 聚合物-纳米金属氧化物复合墨水及其制备方法与应用
CN107104194A (zh) * 2017-05-26 2017-08-29 吉林大学 一种双面发光的无机钙钛矿量子点led及其制备方法
CN108735907A (zh) * 2017-04-21 2018-11-02 Tcl集团股份有限公司 一种qled器件、显示装置及其制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100350314C (zh) * 2004-03-11 2007-11-21 统宝光电股份有限公司 双面显示的液晶显示器装置及双面发光型背光板
US9203030B2 (en) * 2011-05-16 2015-12-01 Georgia Tech Research Corporation Recyclable organic solar cells on substrates comprising cellulose nanocrystals (CNC)
US9076768B2 (en) * 2011-05-16 2015-07-07 Georgia Tech Research Corporation Systems and methods for producing low work function electrodes
CN105304829B (zh) * 2015-11-18 2018-05-08 Tcl集团股份有限公司 一种双面发光量子点发光二极管及其制备方法
KR102511544B1 (ko) * 2015-11-20 2023-03-17 삼성디스플레이 주식회사 광전 소자 및 이의 제조 방법
CN108336107A (zh) * 2017-01-19 2018-07-27 京东方科技集团股份有限公司 有机发光二极管（oled）阵列基板及其制备方法、显示装置
CN107507918B (zh) * 2017-08-30 2019-09-03 电子科技大学 一种钙钛矿发光二极管及其制备方法
CN107994124B (zh) * 2017-11-29 2020-02-21 京东方科技集团股份有限公司 发光二极管及其制备方法、阵列基板、电子装置
CN108493343B (zh) * 2018-04-04 2020-04-24 清华大学 一种钙钛矿薄膜及其制备方法以及该薄膜在光电器件中的应用
CN110387227B (zh) * 2018-04-20 2021-03-05 京东方科技集团股份有限公司 钙钛矿薄膜、钙钛矿电致发光器件及制备方法、显示装置
CN110534653A (zh) * 2018-05-23 2019-12-03 中国科学院苏州纳米技术与纳米仿生研究所 钙钛矿薄膜及其制备方法和应用
CN110534659B (zh) 2018-05-23 2022-09-27 昆明申北科技有限公司 顶发光oled的阳极结构、显示装置及其制造方法
CN110416410A (zh) * 2019-07-11 2019-11-05 重庆文理学院 一种钙钛矿薄膜的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150034930A1 (en) * 2012-03-07 2015-02-05 Osram Opto Semiconductors Gmbh Organic light-emitting device
CN105778619A (zh) * 2014-12-17 2016-07-20 中国科学院苏州纳米技术与纳米仿生研究所 聚合物-纳米金属氧化物复合墨水及其制备方法与应用
CN108735907A (zh) * 2017-04-21 2018-11-02 Tcl集团股份有限公司 一种qled器件、显示装置及其制备方法
CN107104194A (zh) * 2017-05-26 2017-08-29 吉林大学 一种双面发光的无机钙钛矿量子点led及其制备方法

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