WO2018036101A1 - 荧光/磷光混合型白光有机发光二极管 - Google Patents

荧光/磷光混合型白光有机发光二极管 Download PDF

Info

Publication number
WO2018036101A1
WO2018036101A1 PCT/CN2017/071957 CN2017071957W WO2018036101A1 WO 2018036101 A1 WO2018036101 A1 WO 2018036101A1 CN 2017071957 W CN2017071957 W CN 2017071957W WO 2018036101 A1 WO2018036101 A1 WO 2018036101A1
Authority
WO
WIPO (PCT)
Prior art keywords
light emitting
emitting layer
host material
blue
emitting diode
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/CN2017/071957
Other languages
English (en)
French (fr)
Inventor
袁伟
涂爱国
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.)
TCL China Star Optoelectronics Technology Co Ltd
Original Assignee
Shenzhen 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 Shenzhen China Star Optoelectronics Technology Co Ltd filed Critical Shenzhen China Star Optoelectronics Technology Co Ltd
Priority to US15/500,284 priority Critical patent/US10263209B2/en
Publication of WO2018036101A1 publication Critical patent/WO2018036101A1/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
    • 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
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • 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
    • 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
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/27—Combination of fluorescent and phosphorescent emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the invention belongs to the field of organic light emitting diodes, and in particular relates to a fluorescent/phosphorescent hybrid white light organic light emitting diode.
  • white light organic light-emitting diodes can be classified into three types: full fluorescent white light devices, all phosphorescent white light devices, and fluorescent/phosphorescent hybrid white light devices.
  • full fluorescent white light devices the fluorescent dye can only utilize singlet excitons which account for 25% of the total amount of excitons, while the remaining triplet excitons, which account for 75% of the total amount of excitons, cannot be effectively utilized, and finally with thermal radiation.
  • the form is dissipated and cannot contribute to the emission of light. Therefore, the theoretical maximum quantum efficiency is only 25%.
  • the problem encountered by the two devices, the fluorescent/phosphorescent hybrid white light device has undoubtedly become a better choice, which has aroused widespread concern in the industry.
  • the present invention provides a fluorescent/phosphorescent hybrid white light organic light emitting diode.
  • the light emitting layer comprises a blue light emitting layer, a green light emitting layer and a red light emitting layer, wherein the blue light emitting layer comprises a host material and a blue fluorescent material, and the main material of the blue light emitting layer comprises an electronic type host material.
  • the non-spaced fluorescent/phosphorescent hybrid organic light-emitting diode provided by the invention utilizes the long-range migration and endothermic energy transfer of the triplet excitons by rationally regulating the transmission behavior of electron and hole carriers in the respective light-emitting regions. After gradually optimizing the device structure, high-performance WOLEDs are finally realized. The results show that the device has high efficiency and good spectral stability, and the attenuation of efficiency is obviously improved under high brightness, showing good electroluminescence (EL) performance.
  • EL electroluminescence
  • the host material of the red light emitting layer comprises a hole type host material.
  • the host material of the green light-emitting layer comprises a hole-type host material.
  • the host material of the blue light emitting layer further comprises a hole type host material.
  • the host material of the green light emitting layer further comprises an electronic type host material.
  • the electronic type host material is 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPB).
  • the blue fluorescent material is bis[N-(1-naphthyl)-N-phenyl-amino]tetraphenyl (4P-NPD) and/or 4,4'-double (2,2-distyryl)biphenyl (DPVBi).
  • the hole-type host material is 4,4',4"-tris(9-carbazolyl)triphenylamine (TCTA).
  • the thickness of the blue light-emitting layer is preferably 5-15 nm; the thickness of the green light-emitting layer is preferably 5-20 nm; and the thickness of the red light-emitting layer is preferably 2-10 nm.
  • the mass ratio of the blue fluorescent material to the host material is 1:1 to 1:60.
  • the mass ratio of the electron type host material to the hole type material is 0.5:1 to 3:1.
  • the blue light emitting layer comprises TmPyPb and 4P-PND.
  • the blue fluorescent dye 4P-NPD itself is co-doped with the electronic type host material TmPyPb in the same layer by the higher hole transporting property itself, and the layer functions as both a blue light emitting layer and an intermediate regulating layer.
  • the green light emitting layer is on the cathode side. Due to the bipolar transmission characteristics of the blue light layer, the exciton generating region spans the entire blue light emitting layer, broadens the width of the exciton generating region, reduces the concentration of triplet excitons, and can effectively control the roll-off of the device.
  • the mass ratio of TmPyPb to 4P-PND is from 2:1 to 6:1, for example 3:1.
  • the blue light emitting layer comprises TCTA, TmPyPb, and 4P-PND.
  • Cavity body The material TCTA is introduced into the blue light emitting layer, releasing the pressure of the previous 4P-NPD as both a luminescent dye and a host of hole transport, so that the doping ratio of 4P-NPD can be effectively reduced, so that it can specifically act as a luminescent dye. character of.
  • the ratio of the total mass of TCTA and TmPyPb to the mass of 4P-PND is 1:1-60:1.
  • the host material of the red light emitting layer comprises TCTA.
  • the host material of the green light emitting layer comprises TCTA.
  • TCTA is selected as the host material of the red light emitting layer and the green light emitting layer
  • the hole type host material TCTA and the electron type host material TmPyPb are used as a mixed body of the blue light emitting layer, so that the blue layer has the capability of bipolar transmission.
  • the trichromatic light-emitting layer adopts the hole-type material TCTA as a main body, which reduces the potential barrier between the layers, so that the transport of hole carriers and excitons between the respective light-emitting regions is smoother.
  • the exciton recombination zone is located on one side of the luminescent layer and spans the entire blue ray layer. The generated triplet excitons are transmitted to the dye molecules of each layer in a stepwise energy transfer mode, which is beneficial to improve the stability of the spectrum.
  • the red phosphorescent material is Ir(MDQ) 2 (acac), and the mass ratio to the host material is preferably 1:0.05-0.1.
  • the green phosphor material is Ir(ppy) 2 and the mass ratio to the host material is preferably 1:0.05-0.1.
  • the structure of the light emitting layer is such that the red light emitting layer, the blue light emitting layer, and the green light emitting layer are sequentially stacked in the direction from the anode to the cathode.
  • the structure of the light-emitting layer is such that the red light-emitting layer, the green light-emitting layer, and the blue light-emitting layer are sequentially stacked in the direction from the anode to the cathode.
  • the present invention has the following advantageous effects.
  • the roll reduction of the device is mainly due to the use of a bipolar mixed body in the blue layer. This is different from the structure reported in a large number of documents.
  • the exciton generating region is located at the interface of the two functional layers, and the bipolar characteristic makes the exciton generating region.
  • the width of the exciton generating region is widened across the entire blue light emitting layer, which effectively reduces the accumulation of space charge and the concentration of triplet excitons in the exciton generating region at high luminance, thereby suppressing the probability of occurrence of TTA and TPQ, and reducing the probability of occurrence of TTA and TPQ.
  • the roll-off of the device is mainly due to the use of a bipolar mixed body in the blue layer. This is different from the structure reported in a large number of documents.
  • the exciton generating region is located at the interface of the two functional layers, and the bipolar characteristic makes the exciton generating region.
  • the width of the exciton generating region is
  • the device structure has universality, excellent efficiency of the device, stable spectrum and high CRI, which is of great significance for the practical application of fluorescent/phosphorescent hybrid white light devices.
  • Embodiment 1 is an energy level diagram and a structural diagram of an organic light emitting diode according to Embodiment 1.
  • Embodiment 2 is an energy level diagram and a structural diagram of an organic light emitting diode according to Embodiment 2.
  • Embodiment 3 is an energy level diagram and a structural diagram of an organic light emitting diode according to Embodiment 3.
  • the materials used for the light-emitting layer in the preparation process of the device of the present invention are as follows.
  • the anode was selected to use commercial, conductive and light-transmissive ITO (indium tin oxide) glass with an area resistance of 10 ⁇ /cm 2 ; and the cathode was Cs 2 CO 3 /Al.
  • ITO indium tin oxide
  • PEDOT PSS, NPB, TCTA, Ir(MDQ) 2 (acac), Ir(ppy) 2 (acac), 4P-NPD, DPAVBi, TmPyPb, and the structure is as follows:
  • the device's maximum current efficiency, external quantum efficiency, and power efficiency can reach 40.3 cd/A, 16.7%, and 42.3 lm/W, respectively.
  • the maximum current efficiency, external quantum efficiency and power efficiency of the device are 35.2 cd/A, 14.8% and 31.8 lm/W, respectively, CIE color coordinates are (0.48, 0.48), and CRI is 81.
  • the current density J 0 was 53 mA/cm 2 .
  • the device's maximum current efficiency, external quantum efficiency, and power efficiency can reach 43.2 cd/A, 20.3%, and 50.2 lm/W, respectively.
  • the maximum current efficiency, external quantum efficiency and power efficiency of the device are 36.6 cd/A, 17.1% and 34.5 lm/W, CIE color coordinates are (0.48, 0.46), and CRI is 78.
  • the current density J 0 was 78 mA/cm 2 .
  • the maximum current efficiency, external quantum efficiency and power efficiency of the device can reach 45.2 cd/A, 19.0% and 41.7 lm/W, respectively. At 1000 cd/m2, the maximum current efficiency, external quantum efficiency and power efficiency of the device can still be achieved. Maintained at a high level, reaching 40.5 cd / A, 17.0% and 34.3 lm / W, respectively. Evaluation of the degree of roll-off device wherein the key indicators of the current density J 0 105mA / cm 2, greater than reported in the literature 100mA / cm 2, a roll-off effectively improved device.

Landscapes

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

Abstract

一种荧光/磷光混合型白光有机发光二极管，其发光层包括蓝光发光层、绿光发光层和红光发光层，其中该蓝光发光层包含主体材料和蓝色荧光材料，该绿光发光层包括绿色磷光材料，该红光发光层包括红色磷光材料。该蓝光发光层的主体材料包括电子型主体材料。该发光二极管器件效率较高、光谱稳定性好。

Description

荧光/磷光混合型白光有机发光二极管
本申请要求享有2016年8月26日提交的名称为“荧光/磷光混合型白光有机发光二极管”的中国专利申请CN201610735764.4的优先权，其全部内容通过引用并入本文中。
技术领域
本发明属于有机发光二极管领域，具体涉及一种荧光/磷光混合型白光有机发光二极管。
背景技术
根据发光材料的不同，白光有机发光二级管可以分为全荧光白光器件、全磷光白光器件以及荧光/磷光混合型白光器件三类。在全荧光白光器件中，荧光染料仅能利用占激子总量25％的单线态激子，而其余占激子总量75％的三线态激子却不能够被有效利用，最终以热辐射的形式耗散掉，无法对光的发射做出贡献。因此，其内量子效率理论上的最大值仅为25％。对于全磷光白光器件，在重原子耦合作用下，单线态和三线态的能级相互混合，使得原本被禁止的三线态能量缓解并以磷光的形式发出，因此全磷光的白光器件理论上内量子效率可以达到100％。目前，文献中已报道的高效率白光器件均是基于全磷光的白光器件。但是受限于蓝色磷光染料的发光寿命未达理想水准所致，全磷光的白光器件无法满足大多数领域的实际应用。荧光/磷光混合型白光器件，采用稳定的蓝色荧光染料配合以高效的长波长磷光染料，两类发光染料共同作用，使得器件在保证稳定的同时能够获得较高的效率，有效地解决了前两种器件遇到的难题，荧光/磷光混合型白光器件无疑成为了一种更好的选择，引起了业内人士的广泛关注。
目前，荧光/磷光混合型白光器件仍然存在一些亟需解决的问题。1)结构样式过于单调，缺乏新颖的结构设计；2)效率仍然较低，无法同全磷光器件的高效率进行比较；3)在高亮度时，器件效率衰减过快；4)无法在取得高白光质量，即高CRI、良好的CIE以及稳定的光谱同时保证。
发明内容
针对现有技术存在的问题，本发明提供了一种荧光/磷光混合型白光有机发光二极管， 其发光层包括蓝光发光层、绿光发光层和红光发光层，其中所述蓝光发光层包含主体材料和蓝色荧光材料，所述蓝光发光层的主体材料包括电子型主体材料。本发明提供的无间隔层的荧光/磷光混合型有机发光二极管通过合理调控电子、空穴载流子在各个发光区中的传输行为，巧妙地利用三线态激子的长程迁移及吸热能量传递，经逐步优化器件结构后，最终实现了高性能的WOLEDs。结果表明，器件效率较高、光谱稳定性好，并且在高亮度下，效率的衰减得到明显的改善，表现出了很好的电致发光(EL)性能。
根据本发明的优选实施方式，所述红光发光层的主体材料包括空穴型主体材料。
根据本发明的优选实施方式，所述绿光发光层的主体材料包括空穴型主体材料。
根据本发明的优选实施方式，所述蓝光发光层的主体材料进一步包括空穴型主体材料。
根据本发明的优选实施方式，所述绿光发光层的主体材料进一步包括电子型主体材料。
根据本发明的优选实施方式，所述电子型主体材料为1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)。
根据本发明的优选实施方式，所述蓝色荧光材料为双[N-(1-萘基)-N-苯基-氨基]四联苯(4P-NPD)和/或4,4’-双(2,2-二苯乙烯基)联苯(DPVBi)。
根据本发明的优选实施方式，所述空穴型主体材料为4,4′,4″-三(9-咔唑基)三苯基胺(TCTA)。
根据本发明，所述蓝光发光层的厚度优选为5-15nm；所述绿光发光层的厚度优选为5-20nm；所述红光发光层的厚度优选为2-10nm。
根据本发明的优选实施方式，在蓝光发光层中，蓝色荧光材料与主体材料的质量比为1:1-1:60。
根据本发明的优选实施方式，所述蓝光发光层的主体材料中，所述电子型主体材料和所述空穴型材料的质量比为0.5:1-3:1。
根据一些实施例，所述蓝光发光层包括TmPyPb和4P-PND。利用蓝色荧光染料4P-NPD本身所具有的较高空穴传输特性将其与电子型的主体材料TmPyPb共掺杂在同一层内，该层既是蓝光发光层又起到中间调节层的作用。同时将绿光发光层至于阴极一侧。由于蓝光层的双极传输特性，激子产生区横跨整个蓝光发光层，拓宽了激子产生区的宽度，降低了三线态激子的浓度，可以有效控制器件的滚降(roll-off)。优选地，TmPyPb和4P-PND的质量比为2:1-6:1，例如3:1。
根据一些实施例，所述蓝光发光层包括TCTA、TmPyPb和4P-PND。将空穴型主体 材料TCTA引入到蓝光发光层层中，释放了之前4P-NPD既作发光染料又作为空穴传输主体的压力，这样一来可以有效降低4P-NPD的掺杂比例，使其可以专门扮演发光染料的角色。优选地，TCTA和TmPyPb的总质量与4P-PND的质量之比为1:1-60:1。
根据一些实施例，所述红光发光层的主体材料包括TCTA。
根据一些实施例，所述绿光发光层的主体材料包括TCTA。
优选地，选用TCTA作为红光发光层和绿光发光层的主体材料，将空穴型主体材料TCTA和电子型主体材料TmPyPb作为蓝光发光层的混合主体，使得蓝光层具有双极传输的能力。这样一来三基色发光层采用空穴型的材料TCTA作为主体，减少了层与层之间可能存在的势垒，使得空穴载流子和激子在各发光区之间的传输更为顺畅。激子复合区位于发光层一侧，横跨整个蓝光层，产生的三线态激子以阶梯式的能量传递形式传到各层染料分子上辐射复合发光，有利于提升光谱的稳定性。
根据一些实施方式，所述红色磷光材料为Ir(MDQ)2(acac)，与主体材料的质量比优选为1:0.05-0.1。根据一些实施方式，所述绿光磷光材料为Ir(ppy)2，与主体材料的质量比优选为1:0.05-0.1。
根据本发明的一些实施方式，所述发光层的结构为红光发光层、蓝光发光层和绿光发光层沿阳极至阴极的方向依次叠置。
根据本发明的其他实施方式，所述发光层的结构为红光发光层、绿光发光层和蓝光发光层沿阳极至阴极的方向依次叠置。
本发明具有以下有益效果。
1)简化了器件结构，提升了器件效率，在多发光层荧光/磷光混合型白光器件当中消除了常用的间隔层；
2)器件的滚降低，首要原因是蓝光层采用了双极混合主体，这不同于大量文献报道的结构中，激子产生区位于两个功能层的界面处，双极特性使得激子产生区横跨整个蓝光发光层，拓宽了激子产生区的宽度，有效降低了高亮度时激子产生区内空间电荷的积累与三线态激子的浓度，从而抑制了TTA和TPQ发生的几率，降低了器件的滚降。
(3)该器件结构具有普适性，器件优异的效率，稳定的光谱以及较高的CRI，对于荧光/磷光混合型白光器件的实际应用具有重要意义。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例共同用于解释本发明，并不构成对本发明的限制。在附图中：
图1是根据实施例1的有机发光二极管的能级图和结构示意图。
图2是根据实施例2的有机发光二极管的能级图和结构示意图。
图3是根据实施例3的有机发光二极管的能级图和结构示意图。
具体实施方式
下结合实施例对本发明进行详细说明，但本发明并不受下述实施例限定。
本发明器件制备过程中发光层采用的材料如下。
阳极选以用商用的、导电和透光性好的ITO(氧化铟锡)玻璃，面积电阻为10Ω/cm2；阴极选用Cs2CO3/Al。
所使用的其他材料还包括PEDOT：PSS、NPB、TCTA、Ir(MDQ)2(acac)、Ir(ppy)2(acac)、4P-NPD、DPAVBi、TmPyPb，结构如下所示：
Figure PCTCN2017071957-appb-000001
实施例1
双掺杂蓝光层调控颜色的白光有机发光二极管的结构为：ITO/PEDOT/NPB(15nm)/4P-NPD:2wt％Ir(MDQ)2(acac)(5nm)/4P-NPD:TmPyPb＝1:3(10nm)/TmPyPb:8wt％Ir(ppy)2(10nm)/TmPyPb(12nm)/n-ETL/Al，如图1所示。器件的最大电流效率、外量子效率和功率效率分别可以达到40.3cd/A，16.7％和42.3lm/W。在亮度为1000cd/m2时，器件的最大电流效率、外量子效率和功率效率分别为35.2cd/A，14.8％和31.8lm/W，CIE色坐标为(0.48,0.48)，CRI为81，电流密度J0为53mA/cm2。
实施例2
三掺杂蓝光层调控颜色的白光有机发光二极管的结构为ITO/PEDOT/NPB(15nm)/TCTA:3wt％Ir(MDQ)2(acac)(5nm)/TCTA:TmPyPb:4P-NPD＝40wt％:50wt％:10wt％(10nm)/TmPyPb:8wt％Ir(ppy)2(7nm)/TmPyPb(12nm)/n-ETL/Al，如图2所示。器件的最大电流效率、外量子效率和功率效率分别可以达到43.2cd/A，20.3％和50.2lm/W。 在亮度为1000cd/m2时，器件的最大电流效率、外量子效率和功率效率分别为36.6cd/A，17.1％和34.5lm/W，CIE色坐标为(0.48,0.46)，CRI为78，电流密度J0为78mA/cm2。
实施例3
三掺杂蓝光层位于红绿发光层一侧的白光有机发光二极管的结构为ITO/PEDOT/NPB(15nm)/TCTA:4wt％Ir(MDQ)2(acac)(3.5nm)/TCTA:8wt％Ir(ppy)2(5nm)/TCTA:TmPyPb:4P-NPD＝73wt％:25wt％:2wt％(7nm)/TmPyPb(12nm)/n-ETL/Al，如图3所示。器件的最大电流效率、外量子效率和功率效率分别可以达到45.2cd/A，19.0％和41.7lm/W，在亮度为1000cd/m2时，器件的最大电流效率、外量子效率和功率效率仍然可以维持在较高的水平，分别达到40.5cd/A，17.0％和34.3lm/W。评判器件滚降程度的关键指标特征电流密度J0为105mA/cm2，大于文献报道的100mA/cm2，有效改善了器件的滚降。
虽然在上文中已经参考了一些实施例对本发明进行了描述，然而在不脱离本发范围的情况下，可以对其进行各种改进，并且可以用等效物替换其中的部件。尤其是，只要不存在结构冲突，本发明所披露的各个实施例中的各项特征均可通过任意方式相互结合起来使用，在本说明书中未对这些组合的情况进行穷举性的描述仅仅是出于省略篇幅和节约资源的考虑。因此，本发明并不局限于文中公开的特定实施例，而是落入权利要求的范围的所有技术方案。

Claims (20)

  1. 一种荧光/磷光混合型白光有机发光二极管，其发光层包括蓝光发光层、绿光发光层和红光发光层，其中所述蓝光发光层包含主体材料和蓝色荧光材料，所述蓝光发光层的主体材料包括电子型主体材料，所述绿光发光层包括绿色磷光材料，所述红光发光层包括红色磷光材料。
  2. 根据权利要求1所述的有机发光二极管，其中所述红光发光层的主体材料包括空穴型主体材料，和/或所述绿光发光层的主体材料包括空穴型主体材料。
  3. 根据权利要求1所述的有机发光二极管，其中所述蓝光发光层的主体材料进一步包括空穴型主体材料，和/或所述绿光发光层的主体材料进一步包括电子型主体材料。
  4. 根据权利要求1所述的有机发光二极管，其中所述电子型主体材料为1,3,5-三[(3-吡啶基)-3-苯基]苯，和/或所述蓝色荧光材料为双[N-(1-萘基)-N-苯基-氨基]四联苯和/或4,4’-双(2,2-二苯乙烯基)联苯。
  5. 根据权利要求2所述的有机发光二极管，其中所述电子型主体材料为1,3,5-三[(3-吡啶基)-3-苯基]苯，和/或所述蓝色荧光材料为双[N-(1-萘基)-N-苯基-氨基]四联苯和/或4,4’-双(2,2-二苯乙烯基)联苯。
  6. 根据权利要求3所述的有机发光二极管，其中所述电子型主体材料为1,3,5-三[(3-吡啶基)-3-苯基]苯，和/或所述蓝色荧光材料为双[N-(1-萘基)-N-苯基-氨基]四联苯和/或4,4’-双(2,2-二苯乙烯基)联苯。
  7. 根据权利要求2所述的有机发光二极管，其中所述空穴型主体材料为4,4′,4″-三(9-咔唑基)三苯基胺。
  8. 根据权利要求3所述的有机发光二极管，其中所述空穴型主体材料为4,4′,4″-三(9-咔唑基)三苯基胺。
  9. 根据权利要求1所述的有机发光二极管，其中所述蓝光发光层的厚度为5nm-15nm；所述绿光发光层的厚度为5nm-20nm；所述红光发光层的厚度为2nm-10nm。
  10. 根据权利要求2所述的有机发光二极管，其中所述蓝光发光层的厚度为5nm-15nm；所述绿光发光层的厚度为5nm-20nm；所述红光发光层的厚度为2nm-10nm。
  11. 根据权利要求3所述的有机发光二极管，其中所述蓝光发光层的厚度为5nm-15nm；所述绿光发光层的厚度为5nm-20nm；所述红光发光层的厚度为2nm-10nm。
  12. 根据权利要求1所述的有机发光二极管，其中在蓝光发光层中，蓝色荧光材料与主体材料的质量比为1:1-1:60。
  13. 根据权利要求2所述的有机发光二极管，其中在蓝光发光层中，蓝色荧光材料与主体材料的质量比为1:1-1:60。
  14. 根据权利要求3所述的有机发光二极管，其中在蓝光发光层中，蓝色荧光材料与 主体材料的质量比为1:1-1:60。
  15. 根据权利要求3所述的有机发光二极管，其中所述蓝光发光层的主体材料中，所述电子型主体材料和所述空穴型材料的质量比为0.5:1-3:1。
  16. 根据权利要求1所述的有机发光二极管，其中所述发光层的结构为红光发光层、蓝光发光层和绿光发光层沿阳极至阴极的方向依次叠置。
  17. 根据权利要求2所述的有机发光二极管，其中所述发光层的结构为红光发光层、蓝光发光层和绿光发光层沿阳极至阴极的方向依次叠置。
  18. 根据权利要求3所述的有机发光二极管，其中所述发光层的结构为红光发光层、蓝光发光层和绿光发光层沿阳极至阴极的方向依次叠置。
  19. 根据权利要求1所述的有机发光二极管，其中所述发光层的结构为红光发光层、绿光发光层和蓝光发光层沿阳极至阴极的方向依次叠置。
  20. 根据权利要求2所述的有机发光二极管，其中所述发光层的结构为红光发光层、绿光发光层和蓝光发光层沿阳极至阴极的方向依次叠置。
PCT/CN2017/071957 2016-08-26 2017-01-20 荧光/磷光混合型白光有机发光二极管 Ceased WO2018036101A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/500,284 US10263209B2 (en) 2016-08-26 2017-01-20 Fluorescent/phosphorescent mixed white organic light-emitting diode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610735764.4A CN106328818B (zh) 2016-08-26 2016-08-26 荧光/磷光混合型白光有机发光二极管
CN201610735764.4 2016-08-26

Publications (1)

Publication Number Publication Date
WO2018036101A1 true WO2018036101A1 (zh) 2018-03-01

Family

ID=57791449

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/071957 Ceased WO2018036101A1 (zh) 2016-08-26 2017-01-20 荧光/磷光混合型白光有机发光二极管

Country Status (3)

Country Link
US (1) US10263209B2 (zh)
CN (1) CN106328818B (zh)
WO (1) WO2018036101A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328818B (zh) * 2016-08-26 2018-11-20 深圳市华星光电技术有限公司 荧光/磷光混合型白光有机发光二极管
CN107403870B (zh) * 2017-06-21 2019-10-01 武汉华星光电半导体显示技术有限公司 Woled器件
CN108288678B (zh) * 2018-03-29 2023-12-01 佛山科学技术学院 一种双蓝光层杂化白光有机电致发光器件
CN113471376B (zh) * 2021-06-28 2024-03-19 广东聚华印刷显示技术有限公司 发光结构、有机发光二极管和电子设备

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187537A (zh) * 2011-12-31 2013-07-03 昆山维信诺显示技术有限公司 一种高效白光有机电致发光器件
CN103887435A (zh) * 2012-12-21 2014-06-25 厦门天马微电子有限公司 一种有机发光二极管
CN106328818A (zh) * 2016-08-26 2017-01-11 深圳市华星光电技术有限公司 荧光/磷光混合型白光有机发光二极管

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7977862B2 (en) * 2005-12-21 2011-07-12 Lg Display Co., Ltd. Organic light emitting devices
KR20090036504A (ko) * 2007-10-09 2009-04-14 삼성전자주식회사 백색 유기발광소자
CN100484353C (zh) * 2008-01-29 2009-04-29 清华大学 有机电致发光器件
JP5329342B2 (ja) * 2008-09-01 2013-10-30 株式会社半導体エネルギー研究所 発光素子
JP2010114070A (ja) * 2008-10-10 2010-05-20 Canon Inc 白色有機ｅｌ素子
JP5970811B2 (ja) * 2011-12-28 2016-08-17 セイコーエプソン株式会社 発光素子、発光装置および電子機器
CN102738414A (zh) * 2012-06-29 2012-10-17 中国科学院长春应用化学研究所 一种蓝光荧光有机发光二极管及其制备方法
CN102790184B (zh) * 2012-07-31 2016-12-21 昆山维信诺显示技术有限公司 一种琥珀色有机电致发光器件

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187537A (zh) * 2011-12-31 2013-07-03 昆山维信诺显示技术有限公司 一种高效白光有机电致发光器件
CN103887435A (zh) * 2012-12-21 2014-06-25 厦门天马微电子有限公司 一种有机发光二极管
CN106328818A (zh) * 2016-08-26 2017-01-11 深圳市华星光电技术有限公司 荧光/磷光混合型白光有机发光二极管

Also Published As

Publication number Publication date
US20180219168A1 (en) 2018-08-02
CN106328818A (zh) 2017-01-11
US10263209B2 (en) 2019-04-16
CN106328818B (zh) 2018-11-20

Similar Documents

Publication Publication Date Title
TWI673894B (zh) 有機電致發光器件
CN106972111B (zh) 有机发光器件和显示装置
CN104167428A (zh) 有机发光二极管阵列基板及显示装置
KR20180082519A (ko) 유기전계발광소자
CN108011047B (zh) 一种红光有机电致发光器件
CN102751449B (zh) 一种有机发光二极管
KR20150124010A (ko) 백색 유기 발광 소자
CN110190200A (zh) 一种高效高显色指数的纯白光有机电致发光器件及其制备方法
WO2021238448A1 (zh) 有机电致发光器件及阵列基板
CN106654033A (zh) 一种有机发光显示面板以及电子设备
WO2018036101A1 (zh) 荧光/磷光混合型白光有机发光二极管
Li et al. Pure-blue fluorescent organic light-emitting diodes by co-doping a supplementary host material into a light-emitting layer as an electron transport ladder
CN108987594B (zh) 一种有机电致发光二极管和有机电致发光装置
WO2019006784A1 (zh) 一种白光有机电致发光器件和相应的显示面板
CN111416047B (zh) 一种荧光/磷光混合型白光有机发光二极管及其制备方法
CN107591491A (zh) 一种非掺杂白光发光层串联有机电致发光器件及其制作方法
CN106992256A (zh) 一种白色有机电致发光器件
CN108807710A (zh) 非掺杂与掺杂互补白光串联有机电致发光器件及制备方法
TWI540779B (zh) 有機發光裝置
CN108649129A (zh) 一种蓝光有机电致发光器件
CN108682748A (zh) 一种串联白光有机电致发光器件
CN107546248A (zh) 一种非掺杂白光发光层串联有机电致发光器件
CN110034243A (zh) 一种白光有机电致发光器件
CN107302058A (zh) 一种非掺杂白光发光层串联有机电致发光器件
CN107026242B (zh) 一种深蓝光有机铱(ⅲ)配合物oled器件

Legal Events

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

Ref document number: 15500284

Country of ref document: US

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

Ref document number: 17842527

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: 17842527

Country of ref document: EP

Kind code of ref document: A1