WO2017020368A1 - 有机电致发光器件的制备方法及有机电致发光器件 - Google Patents

有机电致发光器件的制备方法及有机电致发光器件 Download PDF

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WO2017020368A1
WO2017020368A1 PCT/CN2015/087961 CN2015087961W WO2017020368A1 WO 2017020368 A1 WO2017020368 A1 WO 2017020368A1 CN 2015087961 W CN2015087961 W CN 2015087961W WO 2017020368 A1 WO2017020368 A1 WO 2017020368A1
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organic electroluminescent
substrate
electroluminescent device
scattering layer
titanium
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French (fr)
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黄辉
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • 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
    • H10K2102/351—Thickness
    • 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
    • H10K2102/361—Temperature
    • 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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes

Definitions

  • the invention relates to the technical field of electric light sources, in particular to a method for preparing an organic electroluminescent device and an organic electroluminescent device.
  • OLED Organic Light-Emitting Diode
  • TFT-LCD thin film transistor-type liquid crystal display devices
  • Dream Display its investment in production equipment is much smaller than LCD display devices, which has won the favor of major display manufacturers. It has become the main force of the third generation display in the display technology field.
  • OLED is in the eve of mass production. With the further development of research and the emergence of new technologies, OLED devices will have a breakthrough development.
  • the OLED device has an anode 200, an organic light-emitting layer 300, and a cathode 400 which are sequentially formed on a substrate 100.
  • the substrate is a light-emitting surface
  • the light exiting path is generally: the organic light-emitting layer 300-anode 200-substrate 100-air, and the light emitted by the organic light-emitting layer 300 can pass through the four-path path to enter the air and enter the light.
  • the human eye To the human eye.
  • the organic light-emitting layer 300 is an organic small molecule material having a refractive index of approximately 1.6-1.7
  • the anode 200 is an indium tin oxide (ITO) film having a refractive index of 1.8
  • the substrate 100 is a glass substrate having a refractive index of 1.5 and air refraction.
  • the ratio is 1.0
  • the light is transmitted from the ITO anode having a refractive index of 1.8 to the glass substrate having a refractive index of 1.5
  • the light is transmitted from the glass substrate 100 having a refractive index of 1.5 to the air having a refractive index of 1.0.
  • the light-tight medium is transmitted to the light-diffusing medium. Therefore, there is a phenomenon of total reflection.
  • the light having an incident angle larger than the critical angle cannot reach the glass substrate due to total reflection, and the light that cannot reach the glass substrate is absorbed and lost inside.
  • the luminous efficiency of a typical OLED device is only about 17%, and most of the light is lost due to the total reflection of the above interface.
  • An object of the present invention is to provide a method for preparing an organic electroluminescent device, on a substrate and A scattering layer is disposed between the anodes, which can improve the light extraction efficiency of the organic electroluminescent device.
  • the titanium dioxide film as a material of the scattering layer is formed by an electrospinning process, and the process conditions are easier to control than the hydrothermal process, and the operability is high.
  • Another object of the present invention is to provide an organic electroluminescence device which can reduce the occurrence of total reflection during the propagation of light emitted from the device to the substrate, and has high light extraction efficiency.
  • the present invention provides a method of preparing an organic electroluminescent device, comprising the steps of:
  • Step 1 The alkyl titanate and the pyrrole-containing polymer are dissolved in a solvent to prepare a solution to obtain a spinning solution;
  • Step 2 providing a stainless steel mesh, using the spinning solution to perform electrospinning on a stainless steel mesh to obtain a titanium-containing electrospun film on a stainless steel mesh;
  • Step 3 after drying, the titanium-containing electrospun film is peeled off from the stainless steel mesh;
  • Step 4 providing a substrate, applying the titanium-containing electrospun film to the substrate, baking at 300-700 ° C, converting the titanium-containing electrospun film into a titanium dioxide film, thereby obtaining a substrate on the substrate Scattering layer
  • Step 5 sequentially forming an anode, an organic electroluminescence structure, and a cathode on the substrate and the scattering layer to obtain the organic electroluminescent device.
  • the alkyl titanate is tetra-n-butyl titanate
  • the pyrrole-containing polymer is polypyrrole or polyvinylpyrrolidone
  • the solvent is water, methanol, ethanol, or butanol.
  • the step 1 further includes adding polyethylene glycol to the solution.
  • the voltage in the electrospinning is 25-50 kV
  • the receiving distance is 10-30 cm
  • the thickness of the obtained titanium-containing electrospun film is not more than 10 ⁇ m
  • the thickness of the scattering layer obtained in the step 4 is Not more than 10 ⁇ m.
  • step 4 baking is performed at 400-600 °C.
  • the substrate provided is a glass substrate.
  • an anode is formed on the substrate and the scattering layer by a sputtering process, and an organic electroluminescent structure and a cathode are formed on the substrate, the scattering layer, and the anode by an evaporation process.
  • the present invention also provides an organic electroluminescent device which is produced by the above-described method for preparing an organic electroluminescent device
  • a substrate a scattering layer sequentially stacked on the substrate, an anode, an organic electroluminescent structure, and a cathode;
  • the material of the scattering layer is a titanium dioxide film.
  • the material of the anode is indium tin oxide; the material of the cathode is metal or alloy metal.
  • the organic electroluminescent structure includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer.
  • the invention also provides a preparation method of an organic electroluminescent device, comprising the following steps:
  • Step 1 The alkyl titanate and the pyrrole-containing polymer are dissolved in a solvent to prepare a solution to obtain a spinning solution;
  • Step 2 providing a stainless steel mesh, using the spinning solution to perform electrospinning on a stainless steel mesh to obtain a titanium-containing electrospun film on a stainless steel mesh;
  • Step 3 after drying, the titanium-containing electrospun film is peeled off from the stainless steel mesh;
  • Step 4 providing a substrate, applying the titanium-containing electrospun film to the substrate, baking at 300-700 ° C, converting the titanium-containing electrospun film into a titanium dioxide film, thereby obtaining a substrate on the substrate Scattering layer
  • Step 5 sequentially forming an anode, an organic electroluminescent structure, and a cathode on the substrate and the scattering layer to obtain the organic electroluminescent device;
  • the alkyl titanate is tetra-n-butyl titanate
  • the pyrrole-containing polymer is polypyrrole or polyvinylpyrrolidone
  • the solvent is water, methanol, ethanol, or butyl. alcohol
  • the voltage in the electrospinning is 25-50 kV
  • the receiving distance is 10-30 cm
  • the thickness of the obtained titanium-containing electrospun film is not more than 10 ⁇ m
  • the scattering layer obtained in the step 4 is obtained.
  • the thickness is not more than 10 ⁇ m
  • an anode is formed on the substrate and the scattering layer by a sputtering process, and an organic electroluminescent structure and a cathode are formed on the substrate, the scattering layer, and the anode by an evaporation process.
  • a scattering layer is disposed between a substrate and an anode of the organic electroluminescent device, and the titanium dioxide film as a material of the scattering layer is formed by an electrospinning process.
  • the electrospun film of titanium is transferred to the substrate and baked, and the electrospinning process is favorable for improving film formation.
  • the uniformity of the titanium-containing electrospun film formed by electrospinning is high, and the film density and thickness can be By adjusting the voltage during electrospinning and the distance between the electrodes, the formed electrospun film containing titanium is easy to move to different substrates, and the operability is high, which is easier than other methods of forming a titanium dioxide film such as hydrothermal method.
  • the organic electroluminescent device of the present invention has a scattering layer between the anode and the substrate, and the scattering layer is a titanium dioxide film, which is obtained by an electrospinning process, and the density and thickness of the film are adjustable, and the substrate is increased.
  • the scattering layer when the light exits from the anode to the substrate, the scattering layer can strongly scatter the light, changing the optical path within the critical angle of total reflection. The incident angle is reduced, so that the light is refracted originally totally reflected, thereby improving the light extraction efficiency of the organic electroluminescent device.
  • FIG. 1 is a schematic view showing an optical path of light propagation in a conventional bottom emission type organic electroluminescent device
  • FIG. 2 is a flow chart of a method of fabricating an organic electroluminescent device of the present invention
  • FIG. 3 is a schematic view showing the second step of the method for preparing an organic electroluminescent device of the present invention
  • FIG. 4 is a schematic view showing a step 3 of a method for preparing an organic electroluminescent device of the present invention
  • Figure 5 is a schematic view showing the step 4 of the method for preparing an organic electroluminescent device of the present invention
  • Figure 6 is a schematic view showing the step 5 of the method for preparing an organic electroluminescent device of the present invention and a schematic cross-sectional structure of the organic electroluminescent device of the present invention.
  • the present invention firstly provides a method for preparing an organic electroluminescent device, comprising the following steps:
  • Step 1 weigh the alkyl titanate, and the polymer containing the pyrrole structure, the alkyl titanate and the pyrrole structure-containing polymer are dissolved in a solvent to prepare a solution to obtain a spinning solution;
  • the alkyl titanate is preferably tetra-n-butyl titanate
  • the polymer containing a pyrrole structure is polypyrrole or polyvinylpyrrolidone
  • the solvent is water, methanol, ethanol, or Other hydrophilic solvents such as butanol.
  • polyethylene glycol may also be added to the spinning solution for modifying the internal structure of the subsequently formed spin coating film.
  • Step 2 as shown in Figure 3, providing a stainless steel mesh 1, stainless steel mesh 1 as a substrate, using a spinning solution on the stainless steel mesh 1 for electrospinning, to obtain a titanium-containing electrospun film 2 on the stainless steel mesh 1;
  • the voltage in the electrospinning is 25-50 kV
  • the receiving distance is the distance between the spinning needle and the stainless steel mesh 1 is 10-30 cm
  • the thickness of the obtained titanium dioxide film is not more than 10 ⁇ m
  • the stainless steel mesh is used as the substrate for electrospinning. Since the stainless steel mesh is a mesh structure, it is easier to tear off the spun electrospun film than other substrates (such as PET, glass), so that the electrospun film is conveniently transplanted. Other substrates without destroying the electrospun film.
  • Step 3 as shown in FIG. 4, after drying, the titanium-containing electrospun film 2 is peeled off from the stainless steel mesh 1;
  • the titanium-containing electrospun film 2 may be infiltrated as appropriate to facilitate tearing it off the stainless steel mesh 1.
  • Step 4 as shown in Figure 5, providing a substrate 10, the titanium-containing electrospun film 2 is applied to the substrate 10, baked at 300-700 ° C, to obtain a scattering layer 20 on the substrate 10;
  • the titanium-containing electrospun film 2 is baked at a high temperature, converted into a titanium dioxide film containing only pure single titanium dioxide crystal, thereby obtaining a scattering layer 20 on the substrate 10;
  • the titanium dioxide crystallinity can be changed by adjusting the baking temperature, and preferably, the titanium-containing electrospun film 2 applied to the substrate 10 is baked at 400 to 600 °C.
  • the thickness of the titanium dioxide film obtained after baking at a high temperature is not more than 10 ⁇ m, that is, the scattering layer 20 on the substrate 10 is not more than 10 ⁇ m.
  • the substrate 10 is provided as a glass substrate.
  • Step 5 as shown in FIG. 6, an anode 30, an organic electroluminescence structure 40, and a cathode 50 are sequentially formed on the substrate 10 and the scattering layer 20 to obtain an organic electroluminescence device.
  • the anode 30 is formed on the substrate 10 and the scattering layer 20 by a sputtering process, and organic electroluminescence is formed on the substrate 10, the scattering layer 20, and the anode 30 by an evaporation process. Structure 40, and cathode 50.
  • the method for preparing an organic electroluminescent device provides a scattering layer between a substrate and an anode of the organic electroluminescent device, a titanium dioxide film as a material of the scattering layer, and a titanium-containing electrospinning formed by an electrospinning process.
  • the film is transferred to the substrate and baked at a high temperature.
  • the electrospinning process is beneficial to improve film formation.
  • the uniformity of the titanium-containing electrospun film formed by electrospinning is higher, and the compactness and thickness of the film can be adjusted by static electricity.
  • the voltage at the time of spinning and the distance between the electrodes are adjusted, and the formed electrospun film containing titanium is easily moved to different substrates, and the operability is high.
  • the electrospinning process is more advanced than the hydrothermal method and the like for forming a titanium dioxide film. Almost control the process conditions, the prepared organic electroluminescent device, when light is emitted from the anode to the substrate from the device, the scattering layer can strongly scatter light, and the optical path in the critical angle of total reflection is changed and reduced. The incident angle refracts the light that originally formed total reflection, thereby improving the light extraction efficiency of the organic electroluminescent device.
  • the present invention further provides an organic electroluminescence device comprising a substrate 10 and a scattering layer sequentially laminated on the substrate 10. 20.
  • the material of the scattering layer 20 is a titanium dioxide film.
  • the thickness of the scattering layer 20 is not more than 10 ⁇ m.
  • the material of the anode 20 is indium tin oxide.
  • the organic electroluminescent structure 40 includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer.
  • the material of the cathode 50 is a metal or an alloy metal.
  • a scattering layer 20 is disposed between the anode 30 and the substrate 10.
  • the scattering layer is a titanium dioxide film, which is obtained by an electrospinning process, and the density and thickness of the film are adjustable, and scattering is increased on the substrate.
  • Layer when light is emitted from the anode to the substrate from the device, the scattering layer can strongly scatter light, change the optical path within the critical angle of total reflection, reduce the incident angle, and cause the light that originally formed total reflection to occur. Refraction, thereby improving the light extraction efficiency of the organic electroluminescent device.
  • a scattering layer is disposed between a substrate and an anode of the organic electroluminescent device, and the titanium dioxide film as a material of the scattering layer is a titanium-containing film formed by an electrospinning process.
  • the electrospun film is transferred to the substrate and baked, and the electrospinning process is favorable for improving film formation.
  • the uniformity of the titanium-containing electrospun film formed by electrospinning is higher, and the film density and thickness can be passed.
  • the organic electroluminescent device of the present invention has a scattering layer between the anode and the substrate, and the scattering layer is a titanium dioxide film, which is obtained by an electrospinning process, the density and thickness of the film are adjustable, and scattering is increased on the substrate.
  • the scattering layer when light is emitted from the anode to the substrate from the device, the scattering layer can strongly scatter light, changing the optical path within the critical angle of total reflection, reducing Angle, so that the light is refracted originally totally reflected, thereby improving the light extraction efficiency of the organic electroluminescent device.

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

提供了一种有机电致发光器件的制备方法及有机电致发光器件。通过该制备方法，在有机电致发光器件的基板与阳极之间设置了散射层，作为散射层材料的二氧化钛膜通过静电纺丝工艺形成，膜的致密性以及厚度可通过调节静电纺丝时的电压以及电极间距离进行调整，因此工艺参数易于调整，可操作性高，可有效提高有机电致发光器件的光提取效率；在该有机电致发光器件中，阳极与基板之间设有散射层，该散射层为二氧化钛膜，通过静电纺丝工艺形成，膜的致密性及厚度可调，由于基板上增加了散射层，当光从器件内由阳极出射到基板时，散射层可对光进行强烈的散射，将在全反射临界角范围内的光路改变，减小了入射角，使本来形成全反射的光线发生折射，从而提高了有机电致发光器件的光提取效率。

Description

有机电致发光器件的制备方法及有机电致发光器件 技术领域
本发明涉及电光源技术领域，尤其涉及一种有机电致发光器件的制备方法及有机电致发光器件。
背景技术
目前，在照明和显示领域中，有机发光二极管(Organic Light-Emitting Diode，OLED)因其低启动电压，轻薄，自发光等自身的特点，而被广泛应用于照明产品以及显示面板中，以满足低能耗，轻薄和面光源等需求。在显示面板行业中，OLED显示装置相较于传统的薄膜晶体管型液晶显示装置(TFT-LCD，Thin Film Transistor-Liquid Crystal Display)，具有十分优异的显示性能，特别是自发光、结构简单、超轻薄、响应速度快、宽视角、低功耗及可实现柔性显示等特性，因此被誉为“梦幻显示器”，再加上其生产设备投资远小于LCD显示装置，得到了各大显示器厂家的青睐，已成为显示技术领域中第三代显示器的主力军。目前OLED已处于大规模量产的前夜，随着研究的进一步深入，新技术的不断涌现，OLED器件必将有一个突破性的发展。
如图1所示，OLED器件具有依次形成于基板100上的阳极200、有机发光层300和阴极400。对于底发光型OLED器件，基板为出光面，光出射的路径一般为，有机发光层300-阳极200-基板100-空气，有机发光层300发出的光经过四段路径才可以达到空气中而入射到人的眼睛。有机发光层300为有机小分子材料，其折射率大致为1.6-1.7，阳极200采用氧化铟锡(ITO)薄膜，其折射率为1.8，基板100为玻璃基板，其折射率为1.5，空气折射率为1.0，那么光从折射率为1.8的ITO阳极传到折射率为1.5的玻璃基板、及光从折射率为1.5的玻璃基板100传到折射率为1.0的空气的过程中，光是从光密介质到光疏介质进行传递，因此，会存在全反射现象，入射角大于临界角的光线由于全反射而不能到达玻璃基板，不能到达玻璃基板的光就会在内部消耗吸收而损失掉。目前，一般的OLED器件的发光效率仅为17％左右，其中大部分的光由于上述界面全反射而损失。
发明内容
本发明的目的在于提供一种有机电致发光器件的制备方法，在基板与 阳极之间设置散射层，能够提高有机电致发光器件光提取效率，作为散射层材料的二氧化钛膜通过静电纺丝工艺形成，较水热法等工艺更容易控制工艺条件，可操作性高。
本发明的目的还在于提供一种有机电致发光器件，可减少器件内出射光传播至基板过程中的全反射的发生，光提取效率高。
为实现上述目的，本发明提供一种有机电致发光器件的制备方法，包括以下步骤：
步骤1、将钛酸烷基酯、以及含吡咯结构的聚合物溶于溶剂中配制成溶液，得到纺丝溶液；
步骤2、提供不锈钢网，使用所述纺丝溶液在不锈钢网上进行静电纺丝，得到不锈钢网上的含钛的电纺膜；
步骤3、干燥后，将所述含钛的电纺膜从不锈钢网上撕下；
步骤4、提供基板，将所述含钛的电纺膜贴敷于基板上，300-700℃下进行烘烤，使所述含钛的电纺膜转化为二氧化钛膜，从而得到位于基板上的散射层；
步骤5、在所述基板、及所述散射层上依次形成阳极、有机电致发光结构、及阴极，得到所述有机电致发光器件。
所述步骤1中，所述钛酸烷基酯为钛酸四正丁酯，含吡咯结构的聚合物为聚吡咯、或聚乙烯吡咯烷酮；所述溶剂为水、甲醇、乙醇、或丁醇。
所述步骤1中还包括在所述溶液中加入聚乙二醇。
所述步骤2中，静电纺丝中的电压为25-50kV，接收距离为10-30cm，所得到的含钛的电纺膜的厚度不大于10μm，所述步骤4中得到的散射层的厚度不大于10μm。
所述步骤4中，400-600℃下进行烘烤。
所述步骤4中，提供的基板为玻璃基板。
所述步骤5中，通过溅射工艺在基板、及所述散射层上形成阳极，通过蒸镀工艺在所述基板、散射层、及阳极上形成有机电致发光结构、及阴极。
本发明还提供一种有机电致发光器件，其由上述的有机电致发光器件的制备方法制成；
包括基板、依次层叠于所述基板上的散射层、阳极、有机电致发光结构、及阴极；
所述散射层的材料为二氧化钛膜。
所述阳极的材料为氧化铟锡；所述阴极的材料为金属或合金金属。
所述有机电致发光结构包括空穴注入层、空穴传输层、有机发光层、电子传输层、及电子注入层。
本发明还提供一种有机电致发光器件的制备方法，包括以下步骤：
步骤1、将钛酸烷基酯、以及含吡咯结构的聚合物溶于溶剂中配制成溶液，得到纺丝溶液；
步骤2、提供不锈钢网，使用所述纺丝溶液在不锈钢网上进行静电纺丝，得到不锈钢网上的含钛的电纺膜；
步骤3、干燥后，将所述含钛的电纺膜从不锈钢网上撕下；
步骤4、提供基板，将所述含钛的电纺膜贴敷于基板上，300-700℃下进行烘烤，使所述含钛的电纺膜转化为二氧化钛膜，从而得到位于基板上的散射层；
步骤5、在所述基板、及所述散射层上依次形成阳极、有机电致发光结构、及阴极，得到所述有机电致发光器件；
其中，所述步骤1中，所述钛酸烷基酯为钛酸四正丁酯，含吡咯结构的聚合物为聚吡咯、或聚乙烯吡咯烷酮；所述溶剂为水、甲醇、乙醇、或丁醇；
其中，所述步骤2中，静电纺丝中的电压为25-50kV，接收距离为10-30cm，所得到的含钛的电纺膜的厚度不大于10μm，所述步骤4中得到的散射层的厚度不大于10μm；
其中，所述步骤5中，通过溅射工艺在基板、及所述散射层上形成阳极，通过蒸镀工艺在所述基板、散射层、及阳极上形成有机电致发光结构、及阴极。
本发明的有益效果：本发明的有机电致发光器件的制备方法，在有机电致发光器件的基板与阳极之间设置散射层，作为散射层材料的二氧化钛膜为通过静电纺丝工艺形成的含钛的电纺膜转移至基板上并经烘烤得到，静电纺丝工艺有利于提高成膜性，通过电纺形成的含钛的电纺膜的均一度较高，膜的致密性以及厚度可通过调节静电纺丝时的电压以及电极间距离进行调整，所形成的含钛的电纺膜易于移动到不同的基板上，可操作性高，较水热法等其他形成二氧化钛膜的方法更容易控制工艺条件；本发明的有机电致发光器件，阳极与基板之间设有散射层，该散射层为二氧化钛膜，通过静电纺丝工艺得到，膜的致密性及厚度可调，基板上增加了散射层，当光从器件内由阳极出射到基板时，散射层可对光进行强烈的散射，将在全反射临界角范围内的光路改变，减小了入射角，使本来形成全反射的光线发生折射，从而提高了有机电致发光器件的光提取效率。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为现有一种底发光型有机电致发光器件内的光线传播的光路示意图；
图2为本发明有机电致发光器件的制作方法的流程图；
图3为本发明有机电致发光器件的制备方法的步骤2的示意图；
图4为本发明有机电致发光器件的制备方法的步骤3的示意图；
图5为本发明有机电致发光器件的制备方法的步骤4的示意图；
图6为本发明有机电致发光器件的制备方法的步骤5的示意图及本发明有机电致发光器件的剖面结构示意图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
请参阅图2，本发明首先提供一种有机电致发光器件的制备方法，包括如下步骤：
步骤1、称取钛酸烷基酯、以及含吡咯结构的聚合物，将钛酸烷基酯、以及含吡咯结构的聚合物溶于溶剂中配制成溶液，得到纺丝溶液；
具体的，所述步骤1中，所述钛酸烷基酯优选钛酸四正丁酯，含吡咯结构的聚合物为聚吡咯、或聚乙烯吡咯烷酮；所述溶剂为水、甲醇、乙醇、或丁醇等其他亲水性溶剂。
具体的，还可以在纺丝溶液中加入聚乙二醇(PEG)，用于修饰后续形成的纺丝膜的内部结构。
步骤2、如图3所示，提供不锈钢网1，不锈钢网1作为衬底，使用纺丝溶液在不锈钢网1上进行静电纺丝，得到不锈钢网1上的含钛的电纺膜2；
具体的，该步骤2中，静电纺丝中的电压为25-50kV，接收距离即纺丝针头与不锈钢网1间的距离为10-30cm，所得到的二氧化钛膜的厚度不大于10μm；
具体的，以不锈钢网作为衬底进行静电纺丝，由于不锈钢网为网状结构，较其他基板(如PET，玻璃)更容易撕下纺好的电纺膜，从而使得电纺膜方便移植于其他基板，同时不会破坏电纺膜。
步骤3、如图4所示，干燥后，将所述含钛的电纺膜2从不锈钢网1上撕下；
具体的，干燥后，可视情况浸润含钛的电纺膜2，以利于将其从不锈钢网1撕下。
步骤4、如图5所示，提供基板10，将所述含钛的电纺膜2贴敷于基板10上，300-700℃下进行烘烤，得到位于基板10上的散射层20；
具体的，该步骤中，含钛的电纺膜2经高温烘烤后，转化为只含有纯净单一的二氧化钛晶体的二氧化钛膜，从而得到位于基板10上的散射层20；
具体的，可通过调整烘烤温度改变二氧化钛结晶性，优选的，400-600℃下对贴敷于基板10上的含钛的电纺膜2进行烘烤。
具体的，经高温烘烤后得到的二氧化钛膜的厚度不大于10微米，即位于基板10上的散射层20不大于10μm。
具体的，该步骤4中，提供的基板10为玻璃基板。
步骤5、如图6所示，在所述基板10、及所述散射层20上依次形成阳极30、有机电致发光结构40、及阴极50，得到有机电致发光器件。
具体的，该步骤5中，通过溅射工艺在基板10、及所述散射层20上形成阳极30，通过蒸镀工艺在所述基板10、散射层20、及阳极30上形成有机电致发光结构40、及阴极50。
本发明提供的有机电致发光器件的制备方法，在有机电致发光器件的基板与阳极之间设置散射层，作为散射层材料的二氧化钛膜，为通过静电纺丝工艺形成的含钛的电纺膜转移到基板上并经高温烘烤得到，静电纺丝工艺有利于提高成膜性，通过电纺形成的含钛的电纺膜的均一度较高，膜的致密性以及厚度可通过调节静电纺丝时的电压以及电极间距离进行调整，所形成的含钛的电纺膜易于移动到不同的基板上，可操作性高，静电纺丝工艺较水热法等其他形成二氧化钛膜的工艺更容易控制工艺条件，所制备的有机电致发光器件，当光从器件内由阳极出射到基板时，散射层可对光进行强烈的散射，将在全反射临界角范围内的光路改变，减小了入射角，使本来形成全反射的光线发生折射，从而提高了有机电致发光器件的光提取效率。
基于以上有机电致发光器件的制备方法，如图6所示，本发明还提供一种有机电致发光器件，包括基板10、依次层叠于所述基板10上的散射层 20、阳极30、有机电致发光结构40、及阴极50。
所述散射层20的材料为二氧化钛膜。
具体的，所述散射层20的厚度不大于10μm。
具体的，所述阳极20的材料为氧化铟锡。
具体的，所述有机电致发光结构40包括空穴注入层、空穴传输层、有机发光层、电子传输层、及电子注入层。
具体的，所述阴极50的材料为金属或合金金属。
本发明的有机电致发光器件，阳极30与基板10之间设有散射层20，该散射层为二氧化钛膜，通过静电纺丝工艺得到，膜的致密性及厚度可调，基板上增加了散射层，当光从器件内由阳极出射到基板时，散射层可对光进行强烈的散射，将在全反射临界角范围内的光路改变，减小了入射角，使本来形成全反射的光线发生折射，从而提高了有机电致发光器件的光提取效率。
综上所述，本发明的有机电致发光器件的制备方法，在有机电致发光器件的基板与阳极之间设置散射层，作为散射层材料的二氧化钛膜为通过静电纺丝工艺形成的含钛的电纺膜转移至基板上并经烘烤得到，静电纺丝工艺有利于提高成膜性，通过电纺形成的含钛的电纺膜的均一度较高，膜的致密性以及厚度可通过调节静电纺丝时的电压以及电极间距离进行调整，所形成的含钛的电纺膜易于移动到不同的基板上，可操作性高，较水热法等其他形成二氧化钛膜的方法更容易控制工艺条件；本发明的有机电致发光器件，阳极与基板之间设有散射层，该散射层为二氧化钛膜，通过静电纺丝工艺得到，膜的致密性及厚度可调，基板上增加了散射层，当光从器件内由阳极出射到基板时，散射层可对光进行强烈的散射，将在全反射临界角范围内的光路改变，减小了入射角，使本来形成全反射的光线发生折射，从而提高了有机电致发光器件的光提取效率。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (14)

  1. 一种有机电致发光器件的制备方法，包括以下步骤：
    步骤1、将钛酸烷基酯、以及含吡咯结构的聚合物溶于溶剂中配制成溶液，得到纺丝溶液；
    步骤2、提供不锈钢网，使用所述纺丝溶液在不锈钢网上进行静电纺丝，得到不锈钢网上的含钛的电纺膜；
    步骤3、干燥后，将所述含钛的电纺膜从不锈钢网上撕下；
    步骤4、提供基板，将所述含钛的电纺膜贴敷于基板上，300-700℃下进行烘烤，使所述含钛的电纺膜转化为二氧化钛膜，从而得到位于基板上的散射层；
    步骤5、在所述基板、及所述散射层上依次形成阳极、有机电致发光结构、及阴极，得到所述有机电致发光器件。
  2. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤1中，所述钛酸烷基酯为钛酸四正丁酯，含吡咯结构的聚合物为聚吡咯、或聚乙烯吡咯烷酮；所述溶剂为水、甲醇、乙醇、或丁醇。
  3. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤1中还包括在所述溶液中加入聚乙二醇。
  4. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤2中，静电纺丝中的电压为25-50kV，接收距离为10-30cm，所得到的含钛的电纺膜的厚度不大于10μm，所述步骤4中得到的散射层的厚度不大于10μm。
  5. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤4中，400-600℃下进行烘烤。
  6. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤4中，提供的基板为玻璃基板。
  7. 如权利要求1所述的有机电致发光器件的制备方法，其中，所述步骤5中，通过溅射工艺在基板、及所述散射层上形成阳极，通过蒸镀工艺在所述基板、散射层、及阳极上形成有机电致发光结构、及阴极。
  8. 一种有机电致发光器件，其由权利要求1中任一项所述的有机电致发光器件的制备方法制成；
    包括基板、依次层叠于所述基板上的散射层、阳极、有机电致发光结构、及阴极；
    所述散射层的材料为二氧化钛膜。
  9. 如权利要求8所述的有机电致发光器件，其中，所述阳极的材料为氧化铟锡；所述阴极的材料为金属或合金金属。
  10. 如权利要求8所述的有机电致发光器件，其中，所述有机电致发光结构包括空穴注入层、空穴传输层、有机发光层、电子传输层、及电子注入层。
  11. 一种有机电致发光器件的制备方法，包括以下步骤：
    步骤1、将钛酸烷基酯、以及含吡咯结构的聚合物溶于溶剂中配制成溶液，得到纺丝溶液；
    步骤2、提供不锈钢网，使用所述纺丝溶液在不锈钢网上进行静电纺丝，得到不锈钢网上的含钛的电纺膜；
    步骤3、干燥后，将所述含钛的电纺膜从不锈钢网上撕下；
    步骤4、提供基板，将所述含钛的电纺膜贴敷于基板上，300-700℃下进行烘烤，使所述含钛的电纺膜转化为二氧化钛膜，从而得到位于基板上的散射层；
    步骤5、在所述基板、及所述散射层上依次形成阳极、有机电致发光结构、及阴极，得到所述有机电致发光器件；
    其中，所述步骤1中，所述钛酸烷基酯为钛酸四正丁酯，含吡咯结构的聚合物为聚吡咯、或聚乙烯吡咯烷酮；所述溶剂为水、甲醇、乙醇、或丁醇；
    其中，所述步骤2中，静电纺丝中的电压为25-50kV，接收距离为10-30cm，所得到的含钛的电纺膜的厚度不大于10μm，所述步骤4中得到的散射层的厚度不大于10μm；
    其中，所述步骤5中，通过溅射工艺在基板、及所述散射层上形成阳极，通过蒸镀工艺在所述基板、散射层、及阳极上形成有机电致发光结构、及阴极。
  12. 如权利要求11所述的有机电致发光器件的制备方法，其中，所述步骤1中还包括在所述溶液中加入聚乙二醇。
  13. 如权利要求11所述的有机电致发光器件的制备方法，其中，所述步骤4中，400-600℃下进行烘烤。
  14. 如权利要求11所述的有机电致发光器件的制备方法，其中，所述步骤4中，提供的基板为玻璃基板。
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