WO2018166094A1 - 一种柔性显示器件及其制备方法 - Google Patents

一种柔性显示器件及其制备方法 Download PDF

Info

Publication number
WO2018166094A1
WO2018166094A1 PCT/CN2017/089546 CN2017089546W WO2018166094A1 WO 2018166094 A1 WO2018166094 A1 WO 2018166094A1 CN 2017089546 W CN2017089546 W CN 2017089546W WO 2018166094 A1 WO2018166094 A1 WO 2018166094A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal layer
layer
display device
flexible display
work function
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/089546
Other languages
English (en)
French (fr)
Inventor
潘彪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan China Star Optoelectronics Technology Co Ltd
Original Assignee
Wuhan China Star Optoelectronics Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan China Star Optoelectronics Technology Co Ltd filed Critical Wuhan China Star Optoelectronics Technology Co Ltd
Priority to US15/564,363 priority Critical patent/US10270055B2/en
Publication of WO2018166094A1 publication Critical patent/WO2018166094A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H10K59/8051—Anodes
    • H10K59/80517—Multilayers, e.g. transparent multilayers

Definitions

  • the invention belongs to the field of display technology, and in particular relates to a novel flexible display device and a preparation method thereof.
  • the organic electroluminescent device is a novel flat panel display device. Compared with a liquid crystal display device (LCD), it has the characteristics of high brightness, active illumination, wide viewing angle, fast response, etc., and is a rising star in the field of flat panel display, showing a broad Development and application prospects.
  • the principle of luminescence of an organic electroluminescent device is that under the action of an external electric field, carriers are injected into the luminescent layer from the electrode to emit light.
  • Organic electroluminescent devices require a high work function and good transparency for the anode material to facilitate light exiting the device.
  • the anode material of the organic electroluminescent device is usually made of Sn 2 doped In 2 O 3 (In 2 O 3 :SnO 2 ), that is, ITO.
  • the conduction band of ITO is mainly composed of the 5s orbital of In and Sn.
  • the valence band is dominated by the 2p orbital of oxygen.
  • the oxygen vacancy and the Sn 4+ substitution doping atom constitute the donor level and affect the carrier concentration in the conduction band. Due to the oxygen vacancies generated in the film during ITO deposition and the doping of Sn 4+ to In 3+ to form a highly degenerate n-type semiconductor, the Fermi level EF is above the conduction band bottom EC, so ITO has Very high carrier concentration and low resistivity.
  • ITO has a wide band gap, so the ITO film has a high transmittance for visible light and near-infrared light. Since ITO has the above excellent electrical conductivity and light transmittance, it is widely used as an anode in electro-optical devices, such as liquid crystal displays (LCDs), organic electroluminescent diodes (OLEDs), quantum dot light-emitting diodes (QLEDs), and Solar cell (OPV).
  • LCDs liquid crystal displays
  • OLEDs organic electroluminescent diodes
  • QLEDs quantum dot light-emitting diodes
  • OOV Solar cell
  • the ITO electrode has the above-mentioned series of advantages, since ITO is a non-stoichiometric compound, the chemical composition of the surface of the ITO film has a great influence on its surface work function.
  • the work function of ITO is 4.5-5.0 eV, which is still lower than that of metals such as Ni (5.4 eV), which is disadvantageous for the injection of holes.
  • the ITO film is very fragile, and it is easily broken even when subjected to bending with less physical stress, and the flexural resistance is poor.
  • the flexible and flexible display device of the present invention has become the mainstream of the future market. So in the emerging product market where wearable devices are gradually emerging Under the wave of the field, ITO materials were gradually eliminated as conductive electrodes in order to meet the needs of the market.
  • the present invention provides a metal electrode which can replace ITO and a flexible OLED device which uses the electrode as an anode layer.
  • Such a flexible display device includes a substrate, an anode layer disposed on the substrate, and a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a hole transport layer disposed on the anode layer from bottom to top, An electron injection layer, a cathode layer and an encapsulation layer, the anode layer comprising a third metal layer disposed on the substrate, and a first metal layer and a second metal disposed on the third metal layer a work function of the first metal layer and the third metal layer is greater than the second metal layer; a work function of the first metal layer and/or the third metal layer is not less than 4.5 eV.
  • a difference between a work function of the second metal layer and a work function of the first metal layer and/or the third metal layer is 0.2 to 0.7 eV.
  • a sum of thicknesses of the first metal layer and the third metal layer is equivalent to a total thickness of the second metal layer.
  • first metal layer and/or the third metal layer have a thickness of 3 to 25 nm
  • second metal layer has a thickness of 6 to 50 nm.
  • the material of the first metal layer and/or the third metal layer is Ni; and the material of the second metal layer is Ag.
  • the invention also provides a preparation method of the flexible display device, comprising the following steps:
  • a third metal layer on the substrate by a vacuum thermal evaporation method; forming a second metal layer on the third metal layer by a coating process, and then vacuum baking and hardening the second layer The metal layer is dried and cured; finally, the first layer is formed on the second metal layer by a vacuum thermal evaporation method.
  • a metal layer wherein a work function of the first metal layer and the third metal layer is greater than the second metal layer; and a work function of the first metal layer and/or the third metal layer is not less than 4.5 eV.
  • a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, a cathode layer, and an encapsulation layer are sequentially formed on the anode layer by vacuum thermal evaporation.
  • a difference between a work function of the second metal layer and a work function of the first metal layer and/or the third metal layer is 0.2 to 0.7 eV.
  • a sum of thicknesses of the first metal layer and the third metal layer is equivalent to a total thickness of the second metal layer.
  • first metal layer and/or the third metal layer have a thickness of 3 to 25 nm
  • second metal layer has a thickness of 6 to 50 nm.
  • the material of the first metal layer and/or the third metal layer is Ni; and the material of the second metal layer is Ag.
  • the invention adopts the metal material with higher work function to prepare the anode layer, and at the same time, the surface of the metal material is surface-treated to obtain the surface of the anode layer with high work function, which can further improve the work function of the anode and improve the injection efficiency of the hole.
  • the metal process is realized by vacuum thermal evaporation, the preparation temperature is low, the process difficulty can be reduced, the yield of the anode layer can be improved, and the device can be improved due to the good bendability of the metal.
  • the degree of flex resistance is more suitable as a flexible light-emitting device.
  • FIG. 1 is a schematic structural view of a flexible display device according to an embodiment of the present invention.
  • FIG. 2 is a flow chart showing the preparation of a flexible display device according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram showing the energy level structure of each material layer of the flexible display device according to the embodiment of the present invention.
  • the present invention provides an improved structure of a flexible OLED device.
  • the flexible display device includes, in order from bottom to top, a substrate 10, an anode layer 20, a hole injection layer 30, a hole transport layer 40, and an organic The light emitting layer 50, the electron transport layer 60, the electron injection layer 70, the cathode layer 80, and the encapsulation layer 90.
  • a work function can be simply understood as the ability of an object to own or capture an electron.
  • the work function of a metal is expressed as the minimum energy required for an electron whose initial energy is equal to the Fermi level to escape from the interior of the metal into the vacuum.
  • the size of the work function marks the strength of electrons bound in the metal. The larger the work function, the less likely the electrons are to leave the metal.
  • the value of the work function is related to the surface condition. As the atomic number increases, the work function also changes periodically.
  • the anode layer 20 of the present invention is a transparent conductive anode having a high work function and suitable for use as a flexible light-emitting device in place of the existing ITO electrode.
  • the anode layer 20 includes a third metal layer 21, a second metal layer 22, and a first metal layer 23 which are stacked on the substrate 10 in this order from bottom to top.
  • the work function of the first metal layer and the third metal layer is greater than the second metal layer; the work function of the second metal layer is between the work function of the first metal layer and/or the third metal layer
  • the difference is 0.2 to 0.7 eV.
  • the metal material work function law of the third metal layer 21, the second metal layer 22, and the first metal layer 23 may be set to: a high work function/low work function/high work function. That is, preferably, the work function of the first metal layer and the third metal layer is greater than the second metal layer, and the metal material selected from the first metal layer and/or the third metal layer has a work function of not less than 4.5 eV.
  • the work function of the second metal layer is lower than 4.5 eV.
  • the choice of metal material is generally carried out in the range of work function of 4.5 ⁇ 5.5eV, which is due to the metal material with too high work function, because it is too active and is not conducive to the stability of device performance.
  • the metal materials of the third metal layer 21 and the first metal layer 23 may be the same.
  • the metal materials of the third metal layer 21, the second metal layer 22, and the first metal layer 23 can be selected as: Ni (work function 4.6 eV), Ag (work function 4.2 eV), Ni (work function 4.6 eV)
  • the obtained anode layer is Ni/Ag/Ni, and its work function can be as high as 5.4 eV.
  • the sum of the thicknesses of the first metal layer and the third metal layer is preferably equivalent to the total thickness of the second metal layer.
  • the thickness of the first metal layer and/or the third metal layer is preferably in the range of 3 to 25 nm, and the thickness of the second metal layer is preferably in the range of 6 to 50 nm.
  • An anode layer is formed on the flexible substrate.
  • a flexible substrate is provided, and the material may be, for example, polyethylene terephthalate (PET), polyamide (PI), polymethyl methacrylate (PMMA), or the like.
  • PET polyethylene terephthalate
  • PI polyamide
  • PMMA polymethyl methacrylate
  • S2 forming a nano silver wire film on the substrate by a coating process, and drying the nano silver wire film by a vacuum baking process (the specific operation is: baking at a temperature of 60-80° for 60-90 seconds) And then curing the nano silver wire film by a hard film process (specifically: baking at a temperature of 150 to 170 ° for 10 to 18 minutes) to obtain a second metal layer having a thickness of 6 nm;
  • a first metal layer is formed on the second metal layer by using the same preparation method as the third metal layer, and has a thickness of 3 nm and a material of Ni.
  • the structure of “high work function/low work function/high work function” formed by alternately stacking three layers of metal nano materials can be obtained through steps S1 to S3. In other embodiments, reference may also be made to the metal material alternating with high and low work functions.
  • the lamination rule, repeating steps S2, S3, forming a metal nano-layer structure of three or more layers, can still achieve the object of the present invention.
  • the Ni metal surface layer of the first metal layer is surface-treated by oxygen plasma.
  • the plasma of oxygen has high oxidizing property and can oxidize impurities on the surface of the first metal layer to achieve the purpose of cleaning the surface of the first metal layer.
  • S5 The photoresist is then coated on the surface-treated first metal layer, and dried and cured.
  • the specific operation is: placing the first metal layer coated with the photoresist in a vacuum oven, baking at a temperature of 60-80 ° for 60-90 seconds, and drying the photoresist to 150-170 °. The temperature is baked for 10 to 18 minutes to cure the photoresist.
  • S8 a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a metal cathode layer are sequentially formed by vacuum thermal evaporation on the anode layer.
  • molybdenum trioxide is used as a hole injection layer
  • 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline (TAPC) is a hole transport layer
  • 4 , 4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) is an exciton barrier layer
  • the host material is N,N'-dicarbazole-3,5-benzene (mCP) doped double ( 4,6-difluorophenylpyridine-N,C2)pyridine hydrazide (FIrpic) and acetylacetonate bis(2-phenylbenzothiazole-C2,N) ruthenium(III) (Ir(bt) 2 (acac) is an organic light-emitting layer
  • 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPB) is an electron transport layer
  • LiF is
  • PET/(Ni/Ag/Ni, 3 nm/6 nm/3 nm)/MoO 3 5 nm)/TAPC (60 nm)/TCTA (5 nm)/mCP: FIrpic: Ir(bt) 2 (acac) (7 wt%: 1 wt%) , 20 nm) / TmPyPB (35 nm) / LiF (1 nm) / Al (100 nm), the "()" content after each functional layer material indicates the concentration or thickness value.
  • the metal anode layer after multilayer metal stacking has a work function of 5.4 eV (after oxygen plasma treatment).
  • the energy level structure of the flexible display device is as shown in FIG. 3, LUMO is the track with the lowest energy level of the unoccupied electrons, and HOMO represents the track with the highest energy level of the occupied electrons, which is called the highest occupied track; FIG. 3 shows that the present invention
  • the anode layer has a high work function, can lower the barrier between the anode layer and the hole transport layer, and improve the hole injection effect, and is very suitable for a transparent electrode layer as a flexible display device.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

提供一种柔性显示器件，包括衬底（10）、设置在衬底上的阳极层（20）、以及，在阳极层上从下至上设置的空穴注入层（30）、空穴传输层（40）、有机发光层（50）、电子传输层（60）、电子注入层（70）、阴极层（80）和封装层（90），阳极层包括设置于衬底上的第三金属层（21），以及，上下层叠设置于第三金属层上的第一金属层（23）、第二金属层（22）；第一金属层、第三金属层的功函数大于第二金属层；第一金属层和/或第三金属层的功函数不小于4.5eV。还提供这种柔性显示器件的制备方法。通过采用较高功函数的金属材料制备阳极层，同时对金属材料表面进行表面处理后得到高功函数的阳极层表面，可以进一步提高阳极的功函数，提高空穴的注入效率。

Description

一种柔性显示器件及其制备方法 技术领域
本发明属于显示技术领域，具体地讲，涉及一种新型的柔性显示器件及其制备方法。
背景技术
有机电致发光器件是一种新型的平板显示器件，与液晶显示器件(LCD)相比，具有亮度高、主动发光、视角宽、响应速度快等特点，是平板显示领域的后起之秀，呈现出广阔的发展和应用前景。有机电致发光器件的发光原理是在外电场作用下，载流子从电极注入到发光层中复合发光。有机电致发光器件对阳极材料要求具有高的功函数和良好的透光度，以利于光从器件中出射。
目前，有机电致发光器件的阳极材料通常采用掺杂SnO2的In2O3(In2O3:SnO2)，即ITO。ITO的导带主要由In和Sn的5s轨道组成，价带是氧的2p轨道占主导地位，氧空位及Sn4+取代掺杂原子构成施主能级并影响导带中的载流子浓度。由于ITO淀积过程中，薄膜中产生的氧空位和Sn4+对In3+的掺杂取代形成高度简并的n型半导体，费米能级EF位于导带底EC之上，因而ITO具有很高的载流子浓度及低电阻率。此外，ITO的带隙较宽，因而ITO薄膜对可见光和近红外光具有很高的透过率。由于ITO具有以上优良的导电性、透光性，因此，在电致光电器件中广泛作为阳极使用，如液晶显示器(LCD)、有机电致发光二极管(OLED)、量子点发光二极管(QLED)和太阳能电池(OPV)。
尽管ITO电极具有上述一系列优点，然而，由于ITO属于非化学计量学化合物，ITO薄膜表面的化学组成，对其表面功函数的影响很大。ITO的功函数为4.5-5.0eV，较Ni(5.4eV)等金属来说仍然偏低，对于空穴的注入不利。同时由于，ITO薄膜非常脆弱，即使在遇到较小物理应力的弯曲也非常容易被破坏，耐挠曲性能较差。而目前可变形可弯曲的显示装置目前柔性的电致发光器件已经成为未来市场的主流方向。因此在可穿戴设备逐渐崛起的新兴产品市 场的浪潮下，ITO材料作为导电电极以无法不能应付市场的需求而逐渐被淘汰。
基于此，有必要提供一种具有高功函数、适合用作柔性发光器件的透明导电阳极来替代ITO。
发明内容
为克服ITO作为导电电极材料时功函数较低和耐挠曲性能较差的问题，本发明提供一种可替代ITO的金属电极和以此电极作为阳极层的柔性OLED器件。
这种柔性显示器件，包括衬底、设置在衬底上的阳极层、以及，在所述阳极层上从下至上设置的空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层、阴极层和封装层，所述阳极层包括设置于所述衬底上的第三金属层，以及，上下层叠设置于所述第三金属层上的第一金属层、第二金属层；所述第一金属层、第三金属层的功函数大于所述第二金属层；所述第一金属层和/或第三金属层的功函数不小于4.5eV。
进一步地，所述第二金属层的功函数与所述第一金属层和/或第三金属层的功函数之间的差值为0.2～0.7eV。
进一步地，所述第一金属层和所述第三金属层的厚度之和与所述第二金属层的总厚度相当。
进一步地，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
进一步地，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
本发明还提供这种柔性显示器件的制备方法，包括如下步骤：
首先通过真空热蒸镀方法在衬底上形成第三金属层；再通过涂布工艺在所述第三金属层上形成第二金属层，然后真空烘烤工艺和坚膜工艺对所述第二金属层进行干燥和固化处理；最后通过真空热蒸镀方法在第二金属层上形成第一 金属层；其中，所述第一金属层、第三金属层的功函数大于所述第二金属层；所述第一金属层和/或第三金属层的功函数不小于4.5eV。
通过等离子体方法对所述第一金属层进行表面除杂处理；
依次通过光刻、固化工艺，以及曝光和显影工艺在所述第一金属层上形成所述柔性显示器件的阳极层的图案；
清洗残余的光刻胶，暴露并使所述阳极层干燥；
在所述阳极层上通过真空热蒸镀的方法依次形成空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层、阴极层以及封装层。
进一步地，所述第二金属层的功函数与所述第一金属层和/或第三金属层的功函数之间的差值为0.2～0.7eV。
进一步地，控制所述真空热蒸镀的速度为
Figure PCTCN2017089546-appb-000001
进一步地，所述第一金属层和所述第三金属层的厚度之和与所述第二金属层的总厚度相当。
进一步地，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
进一步地，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
有益效果：
本发明采用了较高功函数的金属材料制备阳极层，同时对金属材料表面进行表面处理后得到高功函数的阳极层表面，进一步可以提高阳极的功函数，提高空穴的注入效率。
另一方面，由于金属制程采用真空热蒸镀的方法实现，制备温度较低，可以减少制程的难度，提高阳极层的良品率，并且，由于金属的可弯折性较好，可以提高器件的耐挠曲程度，更适合作为柔性发光器件。
附图说明
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：
图1是本发明实施例的柔性显示器件的结构示意图。
图2是本发明实施例的柔性显示器件制备流程图。
图3是本发明实施例的柔性显示器件各材料层的能级结构示意图。
具体实施方式
以下，将参照附图来详细描述本发明的实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。
本发明提供一种柔性OLED器件的改进结构，如图1所示，这种柔性显示器件从下至上依次包括：衬底10、阳极层20、空穴注入层30、空穴传输层40、有机发光层50、电子传输层60、电子注入层70、阴极层80以及封装层90。
功函数可以简单的理解为物体拥有或者抓获电子的能力。金属的功函数表示为一个起始能量等于费米能级的电子，由金属内部逸出到真空中所需要的最小能量。功函数的大小标志着电子在金属中束缚的强弱，功函数越大，电子越不容易离开金属。功函数的值与表面状况有关，随着原子序数的递增，功函数也呈现周期性变化。
其中，本发明的阳极层20是选用具有高功函数、适合用作柔性发光器件的透明导电阳极来替代现有的ITO电极。具体地，如图1所示，所述阳极层20包括从下至上依次层叠设置于衬底10上的第三金属层21、第二金属层22和第一金属层23。所述第一金属层、第三金属层的功函数大于所述第二金属层；所述第二金属层的功函数与所述第一金属层和/或第三金属层的功函数之间的差值为0.2～0.7eV。
例如，第三金属层21、第二金属层22和第一金属层23的金属材质功函数规律可设置为：高功函数/低功函数/高功函数。即，优选所述第一金属层、第三金属层的功函数大于所述第二金属层，且所述第一金属层和/或第三金属层选用的金属材质其功函数不小于4.5eV，第二金属层的功函数低于4.5eV。不过，金属材质的选择一般会在功函数范围为4.5～5.5eV内进行，这是由于具有过高功函数的金属材料，由于过于活泼而不利于器件性能的稳定。第三金属层21和第一金属层23的金属材质可以相同。
具体地，第三金属层21、第二金属层22和第一金属层23的金属材质可选定为：Ni(功函数4.6eV)、Ag(功函数4.2eV)、Ni(功函数4.6eV)，获得的阳极层为Ni/Ag/Ni，其功函数可高达5.4eV。
进一步地，所述第一金属层和所述第三金属层的厚度之和优选与所述第二金属层的总厚度相当。具体地，所述第一金属层和/或所述第三金属层的厚度范围优选为3～25nm，所述第二金属层的厚度范围优选为6～50nm。
下面，结合图2所示，介绍这种阳极层及其形成的柔性OLED的制备方法，包括如下步骤：
在柔性衬底上形成阳极层。
提供一柔性衬底，材质可例如为聚对苯二甲酸乙二醇酯(PET)，聚酰胺(PI)，聚甲基丙烯酸甲酯(PMMA)等任一种。
S1：然后采用真空热蒸镀的方法，控制蒸镀速度为
Figure PCTCN2017089546-appb-000002
利用掩模板子所述衬底上蒸镀Ni金属层，厚度为3nm，形成第三金属层；在蒸镀过程中，真空度应保持在10-5Torr，温度要求保持金属Ni为气态。
S2：通过涂布工艺在所述衬底上形成纳米银线薄膜，再通过真空烘烤工艺使得所述纳米银线薄膜干燥(具体操作为：以60～80°的温度烘烤60～90秒)，然后再通过坚膜工艺对所述纳米银线薄膜进行固化处理(具体操作为：以150～170°的温度烘烤10～18分钟)，获得厚度为6nm的第二金属层；
S3：最后利用与所述第三金属层相同的制备方法，在所述第二金属层上形成第一金属层，厚度为3nm，材质为Ni。
通过步骤S1～S3可获得三层金属纳米材料交替堆叠形成的“高功函数/低功函数/高功函数”的结构，在其他实施例中，还可以参考这种高低功函数的金属材料交替层叠的规律，重复步骤S2、S3，形成三层以上的金属纳米层结构，仍可以达到本发明目的。
S4：多层堆叠的金属纳米层结构形成后，通过氧等离子体对第一金属层的Ni金属表层进行表面处理。氧气的等离子体具有很高的氧化性，能氧化第一金属层表面的杂质，达到清洁第一金属层表面的目的。
S5：然后再在表面处理后的第一金属层上涂布光刻胶，并进行干燥和固化处理。具体操作为：将涂布有所述光刻胶的第一金属层置于真空烤箱，以60～80°的温度烘烤60～90秒使所述光刻胶干燥后，以150～170°的温度烘烤10～18分钟使所述光刻胶固化。
S6：依次通过曝光和显影工艺使所述光刻胶形成所述柔性显示器件(OLED)的阳极层的图案。
S7：清洗残余的所述光刻胶使所述阳极层暴露，通过干燥工艺使所述阳极层干燥。
此时，阳极层制备完成。
S8：在阳极层上通过真空热蒸镀的方法依次形成空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层、金属阴极层。
本发明申请中，例如：三氧化钼作为空穴注入层、4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)为空穴传输层，4,4',4”-三(咔唑-9-基)三苯胺(TCTA)为激子阻隔层，主体材料N,N′-二咔唑-3,5-苯(mCP)掺杂双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱(FIrpic)和乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)(Ir(bt)2(acac))为有机发光层，1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)为电子传输层，LiF为电子注入层，Al为阴极层。
最终形成的柔性显示器件结构如图1所示，其结构还可表示为：
PET/(Ni/Ag/Ni,3nm/6nm/3nm)/MoO3(5nm)/TAPC(60nm)/TCTA(5nm)/mCP: FIrpic:Ir(bt)2(acac)(7wt％:1wt％,20nm)/TmPyPB(35nm)/LiF(1nm)/Al(100nm)，每一功能层材质后的“()”内容表示浓度或厚度数值。
经过多层金属堆叠之后的金属阳极层，其功函数达到5.4eV(经过氧等离子处理之后)。柔性显示器件的能级结构如图3所示，LUMO是未占有电子的能级最低的轨道，HOMO代表已占有电子的能级最高的轨道称为最高已占轨道；从图3可知，本发明的阳极层具有较高的功函数，可以降低阳极层和空穴传输层之间的势垒，改善空穴的注入效果，非常适用于作为柔性显示器件的透明电极层。
虽然已经参照特定实施例示出并描述了本发明，但是本领域的技术人员将理解：在不脱离由权利要求及其等同物限定的本发明的精神和范围的情况下，可在此进行形式和细节上的各种变化。

Claims (13)

  1. 一种柔性显示器件，包括衬底、设置在衬底上的阳极层、以及，在所述阳极层上从下至上设置的空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层、阴极层和封装层，其中，
    所述阳极层包括设置于所述衬底上的第三金属层，以及，上下层叠设置于所述第三金属层上的第一金属层、第二金属层；所述第一金属层、第三金属层的功函数大于所述第二金属层；所述第一金属层和/或第三金属层的功函数不小于4.5eV。
  2. 根据权利要求1所述柔性显示器件，其中，所述第二金属层的功函数与所述第一金属层和/或第三金属层的功函数之间的差值为0.2～0.7eV。
  3. 根据权利要求2所述柔性显示器件，其中，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
  4. 根据权利要求2所述柔性显示器件，其中，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
  5. 一种柔性显示器件的制备方法，其中，包括如下步骤：
    通过真空热蒸镀方法在衬底上形成第三金属层；
    通过涂布工艺在所述第三金属层上形成第二金属层，真空烘烤工艺和坚膜工艺对所述第二金属层进行干燥和固化处理；
    通过真空热蒸镀方法在第二金属层上形成第一金属层；其中，所述第一金属层、第三金属层的功函数大于所述第二金属层；所述第一金属层和/或第三金属层的功函数不小于4.5eV；
    通过等离子体方法对所述第一金属层进行表面除杂处理；
    依次通过光刻、固化工艺，以及曝光和显影工艺在所述第一金属层上形成所述柔性显示器件的阳极层的图案；
    清洗残余的光刻胶，暴露并使所述阳极层干燥；
    在所述阳极层上通过真空热蒸镀的方法依次形成空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层、阴极层以及封装层。
  6. 根据权利要求5所述柔性显示器件的制备方法，其中，所述第二金属层的功函数与所述第一金属层和/或第三金属层的功函数之间的差值为0.2～0.7eV。
  7. 根据权利要求5所述柔性显示器件的制备方法，其中，控制所述热蒸镀速度为
    Figure PCTCN2017089546-appb-100001
  8. 根据权利要求5所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
  9. 根据权利要求6所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
  10. 根据权利要求7所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的厚度为3～25nm，所述第二金属层的厚度为6～50nm。
  11. 根据权利要求5所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
  12. 根据权利要求6所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
  13. 根据权利要求7所述柔性显示器件的制备方法，其中，所述第一金属层和/或所述第三金属层的材质为Ni；所述第二金属层的材质为Ag。
PCT/CN2017/089546 2017-03-16 2017-06-22 一种柔性显示器件及其制备方法 Ceased WO2018166094A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/564,363 US10270055B2 (en) 2017-03-16 2017-06-22 Flexible display device and method of manufacturing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710156304.0 2017-03-16
CN201710156304.0A CN106848102A (zh) 2017-03-16 2017-03-16 一种柔性显示器件及其制备方法

Publications (1)

Publication Number Publication Date
WO2018166094A1 true WO2018166094A1 (zh) 2018-09-20

Family

ID=59143781

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/089546 Ceased WO2018166094A1 (zh) 2017-03-16 2017-06-22 一种柔性显示器件及其制备方法

Country Status (2)

Country Link
CN (1) CN106848102A (zh)
WO (1) WO2018166094A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848102A (zh) * 2017-03-16 2017-06-13 武汉华星光电技术有限公司 一种柔性显示器件及其制备方法
US10270055B2 (en) 2017-03-16 2019-04-23 Wuhan China Star Optoelectronics Technology Co., Ltd. Flexible display device and method of manufacturing the same
CN107863458B (zh) * 2017-10-30 2019-11-15 武汉华星光电半导体显示技术有限公司 Oled基板的制作方法及oled显示装置的制作方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101263744A (zh) * 2005-09-12 2008-09-10 出光兴产株式会社 导电性层叠体及有机el元件
CN103403912A (zh) * 2011-03-08 2013-11-20 E.I.内穆尔杜邦公司 用于照明的有机电子装置
CN106848102A (zh) * 2017-03-16 2017-06-13 武汉华星光电技术有限公司 一种柔性显示器件及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103427029A (zh) * 2012-05-24 2013-12-04 海洋王照明科技股份有限公司 柔性有机发光器件及其制备方法
KR101398448B1 (ko) * 2012-11-29 2014-05-30 삼성디스플레이 주식회사 유기 발광 표시 장치
CN105336869A (zh) * 2014-07-22 2016-02-17 上海和辉光电有限公司 电极结构及oled显示器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101263744A (zh) * 2005-09-12 2008-09-10 出光兴产株式会社 导电性层叠体及有机el元件
CN103403912A (zh) * 2011-03-08 2013-11-20 E.I.内穆尔杜邦公司 用于照明的有机电子装置
CN106848102A (zh) * 2017-03-16 2017-06-13 武汉华星光电技术有限公司 一种柔性显示器件及其制备方法

Also Published As

Publication number Publication date
CN106848102A (zh) 2017-06-13

Similar Documents

Publication Publication Date Title
US10270055B2 (en) Flexible display device and method of manufacturing the same
CN102640318B (zh) 有机发光元件的制造方法、有机发光元件、发光装置、显示面板以及显示装置
US9349967B2 (en) Solar cell and method for manufacturing the same
CN108886101A (zh) 量子点发光二极管及其制造方法、显示面板和显示装置
CN105140411B (zh) 不含ito的qled及其制备方法
CN105206761B (zh) 一种发光二极管及其制备方法
CN110718637A (zh) 一种量子点发光二极管及其制备方法
WO2022061574A1 (zh) 量子点发光二极管及其制备方法、显示装置
JP2010093165A (ja) 電極の製造方法、これを用いた薄膜トランジスタ素子及び有機エレクトロルミネッセンス素子
WO2017088807A1 (zh) 有机电致发光器件及其制作方法、显示装置
KR20120001684A (ko) 투명 전도성막, 이의 제조 방법, 및 이를 이용한 투명전극 및 소자
WO2018166094A1 (zh) 一种柔性显示器件及其制备方法
WO2019010997A1 (zh) 发光二极管及其制备方法
CN111653678A (zh) 量子点发光二极管及其制作方法、显示面板、显示装置
CN106784199A (zh) 全无机qled显示器件及其制备方法
CN115734640A (zh) 薄膜、薄膜的制备方法、光电器件及显示面板
KR20110107447A (ko) 플렉서블 유기 발광 다이오드 및 그 제조 방법
KR101705406B1 (ko) 갈륨을 포함하는 p형 산화물 반도체를 이용한 유기 발광 다이오드 및 이의 제조 방법
Tsai et al. Organic light-emitting diodes with an electro-deposited copper (I) thiocyanate (CuSCN) hole-injection layer based on aqueous electrolyte
CN109427939B (zh) 一种qled器件及其制备方法
CN109390483B (zh) 一种显示设备及其制备方法
CN109390493B (zh) 一种显示设备及其制备方法
CN111129321A (zh) 一种量子点发光二极管及其制备方法
CN109994650B (zh) 一种薄膜及其制备方法、应用
CN112133842A (zh) 量子点发光器件及其制备方法、显示装置

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 15564363

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17900941

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17900941

Country of ref document: EP

Kind code of ref document: A1