WO2014187084A1 - 一种有机电致发光器件及显示装置 - Google Patents

一种有机电致发光器件及显示装置 Download PDF

Info

Publication number
WO2014187084A1
WO2014187084A1 PCT/CN2013/087147 CN2013087147W WO2014187084A1 WO 2014187084 A1 WO2014187084 A1 WO 2014187084A1 CN 2013087147 W CN2013087147 W CN 2013087147W WO 2014187084 A1 WO2014187084 A1 WO 2014187084A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic electroluminescent
transport layer
electron transport
electroluminescent device
layer
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/CN2013/087147
Other languages
English (en)
French (fr)
Inventor
焦志强
孙力
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.)
BOE Technology Group Co Ltd
Original Assignee
BOE Technology Group 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 BOE Technology Group Co Ltd filed Critical BOE Technology Group Co Ltd
Priority to US14/361,056 priority Critical patent/US20150108444A1/en
Publication of WO2014187084A1 publication Critical patent/WO2014187084A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • 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
    • 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
    • H10K85/311—Phthalocyanine

Definitions

  • Embodiments of the present invention relate to an organic electroluminescent device and a display device. Background technique
  • An organic light emitting device is composed of a cathode, an anode, and a hole transporting layer, a light emitting layer and an electron transporting layer disposed between the anode and the cathode.
  • the voltage between the anode and the cathode is loaded to an appropriate value, the holes generated by the anode and the electrons generated by the cathode are respectively transmitted to the light-emitting layer through the hole transport layer and the electron transport layer and combined in the light-emitting layer.
  • the layer generates light
  • the luminescent layer generates light of three primary colors of red, green and blue depending on the constituent materials, and constitutes a basic color of display.
  • the electron mobility of the electron transport layer is low or the energy level barrier of electron injection from the cathode to the electron transport layer is too high, which leads to a small amount of electrons in the light-emitting layer of the organic electroluminescent device, and organic electroluminescence.
  • the number of holes and electrons in the light-emitting layer of the device does not match, and the number of holes is often more than the number of electrons, which results in lower luminous efficiency of the organic electroluminescent device.
  • the material of the electron transport layer has been gradually improved from the early Alq 3 to the later widely used Bphen.
  • new requirements have been placed on the brightness, efficiency, power consumption and manufacturing cost of the device, and the cathode electron injection capability is also higher. .
  • Embodiments of the present invention provide an organic electroluminescence device and a display device that can improve electron injection and transmission without affecting the light-emitting effect and without increasing the cost.
  • an embodiment of the present invention provides the following technical solution: An organic electroluminescent device comprising an anode, a cathode, and a light emitting layer disposed between the anode and the cathode; the organic electroluminescent device further comprising:
  • An electron transport layer disposed between the cathode and the light-emitting layer is doped, and the electron transport layer is doped with a phthalocyanine dye.
  • the phthalocyanine dye has a doping concentration of more than 0% and less than or equal to 70%.
  • the doping concentration of the phthalocyanine dye is 40% or more and 60% or less.
  • the phthalocyanine dye includes one or more of CuPc, ZnPc, F 16 CuPc, CoPc, F 16 CoPc, TiCl 2 Pc, and TiOPc.
  • the main material of the electron transport layer includes Bphen and NBphen.
  • the anode is an indium tin oxide ITO pattern layer.
  • the organic electroluminescent device further includes:
  • a hole transport layer disposed between the anode and the light emitting layer; a hole injection layer disposed between the anode and the hole transport layer, disposed between the electron transport layer and the cathode Inter-electron injection layer.
  • the organic electroluminescent device is a tandem stacked structure.
  • Embodiments of the present invention also provide a display device including the above-described organic electroluminescent device.
  • the organic electroluminescent device and the display device provided by the embodiments of the present invention can significantly improve the electron injection and transmission efficiency of the OLED device by doping the phthalocyanine dye in the electron transport layer, and balance the holes and electrons in the luminescent layer.
  • the quantity significantly increases the luminous efficiency of the device.
  • there is no problem that the metal is diffused to the light-emitting layer, and there is no need to improve the manufacturing equipment, and the driving voltage can be effectively reduced, which reduces the manufacturing cost to some extent.
  • FIG. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the invention
  • FIG. 2 is a diagram showing voltages of an OLED device doped with CuPc in an electron transport layer and an OLED device in a conventional technique under different driving voltages - Current density-brightness curve comparison diagram;
  • FIG. 3 is a schematic diagram showing a comparison of current density-current efficiency curves of an OLED device doped with CuPc in an electron transport layer and an OLED device in a conventional technique at different current densities;
  • FIG. 4 is a schematic diagram showing a comparison of voltage-current density-luminance curves of an OLED device doped with ZnPc in an electron transport layer and an OLED device in a conventional technique at different driving voltages;
  • Fig. 5 is a schematic diagram showing current efficiency-current density curves of an OLED device in which an electron transport layer is doped with ZnPc and an OLED device in a conventional technique at different current densities.
  • an embodiment of the present invention provides an organic electroluminescent device.
  • the organic electroluminescent device includes an anode 11, a cathode 12, and a light-emitting layer 13 disposed between the anode 11 and the cathode 12;
  • An electron transport layer 14 between the cathode 12 and the light-emitting layer 13.
  • the electron transport layer 14 is for transporting electrons generated by the cathode 12 to the light-emitting layer 13, which is doped with a phthalocyanine dye in this embodiment.
  • the electron transport layer in the embodiment of the present invention is a host-guest dopant layer
  • the host material of the electron transport layer may be an electron transport layer material Bphen in the conventional technology, and a guest dopant material. It is a phthalocyanine dye.
  • Bphen is used as a host material of the electron transport layer as an example.
  • the organic electroluminescent device provided by the embodiment of the present invention can significantly improve the electron injection and transmission efficiency of the OLED device by doping the phthalocyanine dye in the electron transport layer, thereby balancing the number of holes and electrons in the luminescent layer.
  • the driving voltage can also be reduced in a device doped with a phthalocyanine dye in an electron transport layer, to some extent Reduce the manufacturing cost of the device.
  • the doping concentration of the phthalocyanine dye is more than 0% or less and 70%, which is calculated as the mass percentage of the electron transport layer occupied by the phthalocyanine dye.
  • the doping concentration refers to a weight percentage.
  • the phthalocyanine dye has a doping concentration of 40% to 60%.
  • the phthalocyanine dye has a doping concentration of 45%.
  • the phthalocyanine dye includes CuPc, ZnPc, F 16 CuPc, CoPc, F 16 CoPc, TiCl 2 Pc or TiOPc.
  • the anode is an ITO (Indium Tin Oxides) pattern layer, and since the ITO as an anode is patterned, the surface thereof is uneven, so that light does not totally reflect on the surface of the anode, and thus, the entire phenomenon occurs.
  • the reflected light can be emitted from the glass, which enhances the light output.
  • the organic electroluminescent device further includes: a hole transport layer 15 disposed between the anode 11 and the light emitting layer 13; a cavity disposed between the anode 11 and the hole transport layer 15.
  • the anode 11 may be a glass substrate with an ITO pattern, and the hole injection layer 16 may be made of a material such as Mo0 3 or F 4 -TCNQ; the hole transport layer 15 may be NPB or
  • the light-emitting layer 13 can be made of a material such as an organic high molecular polymer, an organic small molecule fluorescent or a phosphorescent material, and the light emitting layer can be made of an undoped other monochromatic, mixed color, and white light emitting layer.
  • the electron transport layer 14 may be made of an organic metal chelate such as CuPc or the like; and the electron injection layer 17 may be made of LiF, Liq, CsF or Cs 2 A common electron injecting material such as C0 3 is made; the cathode 12 can be made of A1.
  • a hole blocking layer may be provided between the electron transport layer 14 of the organic electroluminescent device and the light-emitting layer 13.
  • each functional layer may be as follows:
  • the luminescent layer may be a blue-doped luminescent layer, and the blue luminescent layer doped body is MAND (2-methyl-9) , 10-bis(naphthalen-2-yl) anthracene ) , the blue light emitting layer doped guest is DSA-Ph ( l-4-di-[4-(N, N-diphenyl)amino]styryl-benzene ).
  • the anode is an ITO pattern layer having a thickness of 140 nm; the hole injection layer is made of Mo0 3 and having a thickness of 5 nm; the hole transport layer is made of NPB and having a thickness of 40 nm; and the blue light-emitting layer is made of MAND:DSA-Ph Into, thickness is 30 nm; The electron transport layer material is Bphen doped with CuPc, the doping concentration of CuPc is 45%, the thickness is 35 nm, the electron injection layer is made of LiF, the thickness is 1 nm, the cathode is made of A1, and the thickness is 120 nm.
  • the CuPc-doped organic light-emitting device is fabricated as follows: a transparent glass substrate with ITO (face resistance ⁇ 30 ⁇ / ⁇ ), photolithographically formed a ruthenium pattern layer, and then the bismuth glass substrate is sequentially deionized water, acetone, and The solution was washed in an ultrasonic environment in absolute ethanol, and then dried with ⁇ 2 and subjected to treatment with 0 2 plasma. Finally, the processed substrate is placed in an evaporation chamber, and a hole injection layer Mo0 3 is deposited on the ITO pattern layer in a vacuum of less than 5 ⁇ 10 ⁇ 4 Pa by vacuum thermal evaporation.
  • the thickness is 30 nm), the electron buffer layer LiF (thickness is 1 nm), and the cathode A1 (thickness: 120 nm).
  • A1 uses a metal cathode mask and the evaporation rate is 0.3 nm/s
  • the remaining layers each use an open mask and an evaporation rate of 0.1 nm/s.
  • the device has a light-emitting area of 3mm x 3mm.
  • an electron transport layer made of Bphen doped with CuPc or ZnPc is taken as an example, and compared with an electron transport layer made of Bphen in the conventional art.
  • Comparative 1 An electron transport layer made of Bphen doped with CuPc was compared with an electron transport layer made of Bphen in the conventional art.
  • Organic electroluminescent device having an electron transport layer made of Bphen provided in a conventional technique
  • the energy level of Orbital is about -4.2 eV
  • the LUMO level of the electron transport layer (Bphen) is -2.9 eV
  • the LUMO level of the light-emitting layer (MAND:DSA-Ph) is about -2.5 eV; wherein, the electron transport layer Bphen
  • the difference in energy level between (-2.9 eV) and the electron injection layer LiF (-4.2eV) requires a relatively large driving voltage.
  • CuPc is doped in the Bphen of the electron transport layer (the LUMO level is -3.6 eV), which can reduce the LUMO energy level of the electron transport layer, and the electron transport layer and the electron.
  • An appropriate level difference between the implanted layers LiF (-4.2eV) can lower the driving voltage.
  • the electron mobility of CuPc can be as high as 9.04 ⁇ 10" 4 cm 2 /Vs under an electric field of 3.0 X 10 5 V/cm, while the electron mobility of the conventional electron transport material Bphen is 3.0 x 10 5 V/
  • the electric field of cm is 4.2 10_ 4 cm 2 /Vs, and the electron transport capacity of CuPc is much higher than that of Bphen.
  • the ability to use an organic electroluminescent device made of an electron transport layer made of Bphen doped Bphen has better electron injection and transport efficiency.
  • the performance of the above-described CuPc-doped electron transport layer provided by the present invention and the electron transport layer provided by the conventional technique are compared by experimental measurement.
  • the photoelectric characteristics of the organic electroluminescent device at different CuPc doping concentrations were measured, and the measurement results shown in Table 1 were obtained.
  • the brightness of the organic electroluminescent device satisfies the performance requirement as long as it reaches 1000 cd/m 2 . It is.
  • the performance of the organic electroluminescent device is identified by the maximum current efficiency. It can be seen from Table 1 that the electron transport layer is doped with CuPc organic electroluminescent device (the doping concentration of CuPc is 10%, 20%).
  • the performance of the organic electroluminescent device is better than that of the organic electroluminescent device (CuPc doping concentration of 0%) in which the electron transport layer is not doped with CuPc, and the doping concentration of CuPc is 45%. The most efficient and best performance.
  • FIG. 1 and FIG. 3 show a comparison of performance of an organic electroluminescent device according to the present invention and an organic electroluminescent device of the conventional art when the doping concentration of CuPc is 45%, wherein FIG. 2 illustrates The voltage-current density and voltage-luminance curves of the two organic electroluminescent devices at different driving voltages.
  • Figure 3 illustrates current density-current efficiency plots for two organic electroluminescent devices at different current densities.
  • the organic electroluminescent device provided by the embodiment of the present invention uses an electron made of Bphen doped with CuPc, relative to a conventional organic electroluminescent device using an electron transport layer made of Bphen.
  • the transmission layer has a significant increase in current density and brightness, which indicates that the electron injecting ability of the organic electroluminescent device is significantly improved.
  • the maximum brightness of the organic electroluminescent device is increased from 26,700 cd/m 2 to 53170 cd/m 2 , and the increase is about 99.2%; and the maximum current efficiency increased from 8.98cd/A to 15.9cd/A, an increase of approximately 65.9%. It can be seen from the above that the organic electroluminescent device using the electron transport layer made of CuPc doped with Bphen has a larger luminescent property than the conventional organic electroluminescent device using the electron transport layer made of Bphen. Upgrade.
  • Comparison 2 An electron transport layer made of Bphen doped with ZnPc, and the conventional technique
  • the electron transport layer made of Bphen was compared.
  • the present embodiment provides an organic light-emitting device having an electron transport layer made of Bphen doped with ZnPc.
  • the materials and thicknesses of the other functional layers are different from those described above except that the material doped by the electron transport layer is different.
  • the organic electroluminescent device of the electron transport layer made of Bphen with CuPc is the same.
  • the LUMO level of ZnPc doped into Bphen (-2.9 eV) in the electron transport layer is -3.3 eV, and the LUMO level of the electron transport layer can also be lowered, so that the electron transport layer and the electron injection layer LiF (-4.2 eV) The difference in energy level between them is appropriate to help reduce the driving voltage.
  • the photoelectric characteristics of the organic electroluminescent device at different ZnPc doping concentrations were measured, and the measurement results shown in Table 2 were obtained.
  • the brightness of the organic electroluminescent device satisfies performance requirements as long as it reaches 1000 cd/m 2 .
  • the performance of the organic electroluminescent device is identified by the maximum current efficiency. From Table 2, the organic electroluminescent device with the transport layer doped with ZnPc can be seen.
  • the doping concentration of ZnPc is 10%, 20% 70%), which is better than that of the organic electroluminescent device (the doping concentration of ZnPc is 0%) of the undoped ZnPc of the transport layer, and the doping concentration of ZnPc is At 45%, organic electroluminescent devices have the highest current efficiency and the best performance.
  • Table 2 4 and 5 show voltage-current density, voltage-luminance curves of two organic electroluminescent devices according to the organic electro-sensitive driving voltage of the present invention when the doping concentration of ZnPc is 45%.
  • Figure 5 shows current efficiency-current density plots for two organic electroluminescent devices at different current densities.
  • the organic electroluminescent device using the electron transport layer made of Bphen doped with ZnPc also has an organic light-emitting property higher than that of the electron transport layer made of Bphen. Light-emitting devices have been greatly improved.
  • the experimental results show that after the other phthalocyanine dye is doped into the electron transport layer made of Bphen, the electron transport rate of the organic electroluminescent device including the electron transport layer is also greatly improved.
  • the phthalocyanine dye includes one or more of CuPc, ZnPc, F 16 CuPc, CoPc, F 16 CoPc, TiCl 2 Pc, and TiOPc.
  • the current efficiency of the electron transport layer doped with the phthalocyanine dye is greatly improved, and the photoelectric performance and luminous efficiency are improved. It will be understood by those skilled in the art that when a phthalocyanine dye is doped into an electron transport layer which is made of other materials as a host material, the electron transfer rate of the organic electroluminescent device including the electron transport layer is also greatly increased. Improvement.
  • the main materials that can be used as the electron transport layer include Bphen, NBphen (2,9-bis(naphthalen-2-yl)-4,7-diphenyl- 1 , 10-phenanthroline ) and TPBi ( 2,2',2"-( One or more of 1 , 3,5-benzinetriyl)-tris( 1 -phenyl- 1 -Hbenzimidazole) .
  • the organic electroluminescent device provided by the embodiments of the present invention may also adopt a tandem stacked structure.
  • the tandem stacked organic electroluminescent device shares an anode and a cathode, and a plurality of devices are connected in series, which can improve the luminous efficiency of the organic electroluminescent device and prolong the life of the device.
  • An embodiment of the present invention further provides a display device, where the display device includes the above organic electroluminescent device, and the display device may be an OLED display, an OLED display panel, a digital camera, a mobile phone, a tablet computer, or an electronic paper. A product or part that displays a function.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

一种有机电致发光器件，包括阳极（11），阴极（12），设置在阳极（11）和阴极（12）之间的发光层（13）；设置在阴极（12）与发光层（13）之间的电子传输层（14），电子传输层（14）中掺杂有酞菁类染料。一种包括有机电致发光器件的显示装置。

Description

一种有机电致发光器件及显示装置 技术领域
本发明的实施例涉及一种有机电致发光器件及显示装置。 背景技术
有机电致发光器件 ( Organic Light Emitting Device,筒称 OLED )由阴极、 阳极、 以及设置在所述阳极和阴极之间的空穴传输层、 发光层与电子传输层 组成。 当阳极和阴极之间的电压加载至适当值时， 阳极产生的空穴和阴极产 生的电子就会分别通过空穴传输层和电子传输层传输至发光层并在发光层中 结合， ^^光层产生光， 发光层因组成材料不同而产生红、 绿和蓝三原色的 光， 构成显示的基本色彩。
研究认为， 由于电子传输层的电子迁移率较低或者电子由阴极注入到电 子传输层的能级障碍太高， 会导致有机电致发光器件的发光层中的电子数量 较少， 有机电致发光器件的发光层中空穴和电子的数量不匹配， 往往是空穴 数多于电子数， 这就造成有机电致发光器件的发光效率较低。
电子传输层的材料从早期的 Alq3到后来普遍采用的 Bphen, 其电子注入 能力逐步得到有效的提升。 但是随着有机发光材料体系的不断完善， 以及有 机电致发光器件应用领域的延伸， 对于器件的亮度、 效率和功耗以及制造成 本有了新的要求， 对于阴极电子注入能力也有更高的要求。
近来出现了一种有机电致发光器件， 该有机电致发光器件通过在电子传 输层的 Bphen中掺杂 Li或者 Cs等金属， 来提高电子的注入与传输， 但是由 于金属的扩散性很高， 如果扩散至发光层中将会形成发光的淬熄中心， 影响 发光效果； 而且 Li和 Cs的化学反应性高， 需要特殊的装料和蒸镀设备， 增 加制作成本。 发明内容
本发明的实施例提供了一种有机电致发光器件及显示装置， 可以在不影 响发光效果和不增加成本的情况下提高电子的注入与传输。 为实现上述目的， 本发明的实施例提供了如下技术方案： 一种有机电致发光器件， 包括阳极、 阴极、 设置在阳极和阴极之间的发 光层； 该有机电致发光器件还包括：
设置在阴极与发光层之间的电子传输层， 电子传输层中掺杂有酞菁类染 料。
例如， 所述酞菁类染料的掺杂浓度为大于 0%小于等于 70%。
例如， 所述酞菁类染料的掺杂浓度为大于等于 40%小于等于 60%。
例如， 所述酞菁类染料包括 CuPc、 ZnPc、 F16CuPc、 CoPc、 F16CoPc、 TiCl2Pc和 TiOPc中的一种或多种。
电 子 传 输 层 的 主 体 材 料 包 括 Bphen 、 NBphen
( 2,9-bis(naphthalen-2-yl)-4,7-diphenyl- 1 , 10-phenanthroline ) 和 TPBi ( 2,2',2"-(l,3,5-benzinetriyl)-tris(l-phenyl-l-Hbenzimidazole) ) 中的一种 或多种。
例如， 所述阳极为氧化铟锡 ITO图案层。
例如， 所述有机电致发光器件还包括：
设置在所述阳极与所述发光层之间的空穴传输层； 设置在所述阳极与所 述空穴传输层之间的空穴注入层， 设置在所述电子传输层与所述阴极之间的 电子注入层。
例如， 所述有机电致发光器件为串联叠层式结构。
本发明的实施例还提供了一种显示装置，包括上述的有机电致发光器件。 本发明的实施例提供的有机电致发光器件及显示装置， 通过在电子传输 层中掺杂酞菁类染料， 可以明显提高 OLED器件的电子注入与传输效率， 平 衡发光层中的空穴和电子数量， 明显提高器件的发光效率。 且不存在金属扩 散至发光层的问题， 也不需要改进制作设备， 还可以有效降低驱动电压， 在 一定程度上降低了制造成本。 附图说明
为了更清楚地说明本发明实施例的技术方案， 下面将对实施例的附图作 筒单地介绍，显而易见地，下面描述中的附图仅仅涉及本发明的一些实施例， 而非对本发明的限制。 图 1为根据本发明实施例的一种有机电致发光器件的剖面结构示意图； 图 2为在不同驱动电压下， 电子传输层掺杂有 CuPc的 OLED器件与惯 常技术中的 OLED器件的电压-电流密度-亮度曲线对比示意图；
图 3为在不同电流密度下， 电子传输层掺杂有 CuPc的 OLED器件与惯 常技术中的 OLED器件的电流密度-电流效率曲线对比示意图；
图 4为在不同驱动电压下， 电子传输层掺杂有 ZnPc的 OLED器件与惯 常技术中的 OLED器件的电压-电流密度-亮度曲线对比示意图； 以及
图 5为在不同电流密度下， 电子传输层掺杂有 ZnPc的 OLED器件与惯 常技术中的 OLED器件的电流效率-电流密度曲线对比示意图。 具体实施方式
为使本发明实施例的目的、 技术方案和优点更加清楚， 下面将结合本发 明实施例的附图，对本发明实施例的技术方案进行清楚、 完整地描述。显然， 所描述的实施例是本发明的一部分实施例， 而不是全部的实施例。 基于所描 述的本发明的实施例， 本领域普通技术人员在无需创造性劳动的前提下所获 得的所有其他实施例， 都属于本发明保护的范围。
本发明实施例提供了一种有机电致发光器件， 如图 1所示， 所述有机电 致发光器件包括阳极 11、 阴极 12、 设置在阳极 11和阴极 12之间的发光层 13; 以及设置在所述阴极 12与发光层 13之间的电子传输层 14。 所述电子传 输层 14用于将阴极 12产生的电子传输至发光层 13,在该实施例中所述电子 传输层中掺杂有酞菁类染料。
在这里需要说明的是， 本发明的实施例中的电子传输层是主客体掺杂材 料层， 所述电子传输层的主体材料可以是惯常技术中的电子传输层材料 Bphen等， 客体掺杂材料为酞菁类染料。 在本发明的实施例中， 以 Bphen为 电子传输层的主体材料为例进行说明。
本发明的实施例提供的有机电致发光器件， 通过在电子传输层中掺杂酞 菁类染料， 可以明显提高 OLED器件的电子注入与传输效率， 进而平衡发光 层中的空穴和电子数量， 明显提高器件的发光效率。 由于电子传输层中没有 掺杂金属， 金属扩散至发光层的问题不再存在， 也不需要改进制作设备。 在 电子传输层中掺杂酞菁类染料的器件中还可以降低驱动电压， 在一定程度上 降低了器件的制造成本。
例如， 所述酞菁类染料的掺杂浓度为大于 0%小于等于 70%, 按酞菁类 染料所占电子传输层的质量百分比计算。 在本文中， 所述掺杂浓度指的是重 量百分比。
例如， 所述酞菁类染料的掺杂浓度为 40%-60%。
例如， 所述酞菁类染料的掺杂浓度为 45%。
例如， 所述酞菁类染料包括 CuPc、 ZnPc、 F16CuPc、 CoPc、 F16CoPc、 TiCl2Pc或 TiOPc。
例如， 所述阳极为 ITO ( Indium Tin Oxides, 氧化铟锡） 图案层， 由于 作为阳极的 ITO被图案化， 其表面高低不平， 使光在阳极表面不会发生全反 射， 这样， 本来会发生全反射的光能够从玻璃中射出， 可以增强光输出。
可选的， 如图 1所示，有机电致发光器件还包括： 设置在阳极 11与发光 层 13之间的空穴传输层 15; 设置在阳极 11与空穴传输层 15之间的空穴注 入层 16, 设置在电子传输层 14与阴极 12之间的电子注入层 17。
在本发明的实施例中， 阳极 11可以为带有 ITO图案的玻璃基板， 空穴 注入层 16可以由 Mo03或 F4-TCNQ等材料制成；所述空穴传输层 15可以由 NPB或 TPD等材料制成； 所述发光层 13可以由有机高分子聚合物、 有机小 分子荧光或磷光材料等材料制成， 发光层即可采用非掺杂其他单色、 混合色 以及白色的发光层， 也可以采用掺杂其他单色、 混合色以及白色的发光层； 电子传输层 14可以由有机金属螯合物制成， 如 CuPc等； 电子注入层 17可 以由 LiF、 Liq、 CsF或 Cs2C03等常见电子注入材料制成； 所述阴极 12可以 由 A1制成。
例如， 当电子传输层 14不能 ^艮好地阻挡空穴时，有机电致发光器件的电 子传输层 14和发光层 13之间还可以设置空穴阻挡层。
示例的， 本发明实施例提供的有机电致发光器件中， 各功能层可以如下 所述： 发光层可以为掺杂蓝色的发光层， 蓝光发光层掺杂主体为 MAND ( 2-methyl-9, 10-bis(naphthalen-2-yl) anthracene ) , 蓝光发光层掺杂客体为 DSA-Ph ( l-4-di-[4-(N, N-diphenyl)amino]styryl-benzene )。 其中， 阳极为 ITO 图案层， 厚度为 140nm; 空穴注入层由 Mo03制成， 厚度为 5nm; 空穴传输 层由 NPB制成， 厚度为 40nm; 蓝色发光层由 MAND:DSA-Ph制成， 厚度为 30nm; 电子传输层材料为掺杂 CuPc的 Bphen, CuPc的掺杂浓度为 45%, 厚 度为 35nm, 电子注入层由 LiF制成， 厚度为 lnm, 阴极由 A1制成， 厚度为 120nm。
掺杂 CuPc的有机发光器件的制作方法如下： 带有 ITO (其面电阻 <30Ω/ □)的透明玻璃基底， 经过光刻形成 ΙΤΟ图案层， 然后将 ΙΤΟ玻璃基底依次 在去离子水、 丙酮和无水乙醇中超声环境中清洗， 结束后用 Ν2吹干并进行 02 plasma (等离子体）的处理。 最后将处理好的基片置于蒸镀腔室中， 在低 于 5x lO-4Pa的真空中， 通过真空热蒸镀的方式， 在 ITO图案层上依次沉积空 穴注入层 Mo03(厚度为 5nm), 空穴传输层 NPB(厚度为 40nm) , 蓝光发光层 MAND:DSA-Ph(3%) (厚度为 30nm), 电子传输层 Bphen: CuPc ( CuPc 的掺 杂浓度为 45% ) (厚度为 30nm), 电子緩沖层 LiF (厚度为 lnm), 阴极 A1 (厚度 为 120nm)。 上述蒸镀过程中， 除 A1使用金属阴极掩膜版（ metal mask )且蒸 发速率为 0.3nm/s夕卜， 其余各层均使用开放掩膜版 (open mask)且蒸发速率为 0.1nm/s; 器件的发光面积为 3mm x 3mm。
在下文中， 以由掺杂有 CuPc或 ZnPc的 Bphen制成的电子传输层为例， 与惯常技术中的由 Bphen制成的电子传输层进行比较。
对比 1 : 由掺杂有 CuPc的 Bphen制成的电子传输层， 与惯常技术中的 由 Bphen制成的电子传输层进行比较。
在惯常技术中提供的具有由 Bphen制成的电子传输层的有机电致发光器
Orbital )能级大约为 -4.2eV, 电子传输层（ Bphen )的 LUMO能级为 -2.9 eV, 发光层（MAND:DSA-Ph ) 的 LUMO能级大约为 -2.5eV; 其中， 电子传输层 Bphen ( -2.9 eV )与电子注入层 LiF ( -4.2eV )之间的能级差大， 需要比较大 的驱动电压。 而本发明实施例提供的有机电致发光器件中， 在电子传输层的 Bphen中掺杂 CuPc ( LUMO能级为 -3.6eV ) , 可以降低电子传输层的 LUMO 能级， 使电子传输层与电子注入层 LiF ( -4.2eV )之间具有适当的能级差， 可 以降低驱动电压。
另一方面， CuPc的电子迁移率在 3.0 X 105V/cm的电场下可高达 9.04 χ 10"4cm2/Vs, 而惯常的电子传输材料 Bphen的电子迁移率在 3.0 x 105V/cm 的 电场下为 4.2 10_4cm2 /Vs, CuPc的电子传输能力远高于 Bphen的电子传输 能力， 即采用由掺杂 CuPc的 Bphen制成的电子传输层的有机电致发光器件 具有更好的电子注入与传输效率。
下面通过实验测量对上述本发明提供的掺杂 CuPc的电子传输层和惯常 技术提供的电子传输层的性能进行比较。 测量不同 CuPc掺杂浓度下的有机 电致发光器件的光电特性， 获得表 1所示的测量结果， 通常情况下， 所述有 机电致发光器件的亮度只要达到 1000 cd/m2就满足性能要求了。 一般情况下 所述有机电致发光器件的性能由最大电流效率来标识， 由表 1可以看出电子 传输层掺杂了 CuPc的有机电致发光器件 (CuPc的掺杂浓度为 10%, 20%
70%), 比电子传输层未掺杂 CuPc的有机电致发光器件 (CuPc的掺杂浓度为 0%)的性能要好，且 CuPc的掺杂浓度为 45%时，有机电致发光器件的电流效 率最大， 具有最好的性能。
Figure imgf000008_0001
表 1 图 2和图 3示出了当 CuPc的掺杂浓度为 45%时根据本发明的有机电致 发光器件与惯常技术中的有机电致发光器件的性能对比图， 其中， 图 2图示 了两种有机电致发光器件在不同的驱动电压下的电压-电流密度以及电压-亮 度曲线图。图 3图示了两种有机电致发光器件在不同电流密度下的电流密度- 电流效率曲线图。 从图中可以看出， 相对于采用由 Bphen制成的电子传输层 的惯常有机电致发光器件， 本发明的实施例所提供的有机电致发光器件采用 由掺杂 CuPc的 Bphen制成的电子传输层， 其电流密度和亮度有了很明显的 增加， 这表明有机电致发光器件的电子注入能力得到了显著提高。 有机电致 发光器件的最大亮度从 26700cd/m2提高到了 53170cd/m2， 提升幅度约为 99.2%; 而最大电流效率则从 8.98cd/A提高到了 15.9cd/A, 提升幅度约为 65.9%。 由上可知，采用由 Bphen中掺杂 CuPc所制成的电子传输层的有机电 致发光器件的发光性能比惯常的采用由 Bphen制成的电子传输层的有机电致 发光器件有了很大的提升。
对比 2: 由掺杂有 ZnPc的 Bphen制成的电子传输层， 与惯常技术中由
Bphen制成的电子传输层进行比较。
本实施例提供了具有由掺杂有 ZnPc的 Bphen制成的电子传输层的有机 发光器件， 除电子传输层掺杂的材料不同外， 其他各功能层的材料和厚度均 与上述具有由掺杂有 CuPc的 Bphen制成的电子传输层的有机电致发光器件 相同。
掺杂到电子传输层中的 Bphen ( -2.9 eV ) 中的 ZnPc的 LUMO能级为 -3.3eV, 也可以降低电子传输层的 LUMO能级， 使电子传输层与电子注入层 LiF ( -4.2eV )之间的能级差适当， 有利于降低驱动电压。
测量不同 ZnPc掺杂浓度下的有机电致发光器件的光电特性， 获得表 2 所示的测量结果。 通常情况下， 所述有机电致发光器件的亮度只要达到 1000 cd/m2就满足性能要求了。一般情况下所述有机电致发光器件的性能由最大电 流效率来标识， 由表 2 可以看出传输层掺杂了 ZnPc 的有机电致发光器件
(ZnPc的掺杂浓度为 10%, 20% 70%), 比传输层未掺杂 ZnPc的有机电 致发光器件 (ZnPc的掺杂浓度为 0%)的性能要好，且 ZnPc的掺杂浓度为 45% 时， 有机电致发光器件的电流效率最大， 具有最好的性能。
Figure imgf000009_0001
表 2 图 4和图 5示出了当 ZnPc的掺杂浓度为 45%时根据本发明的有机电致 同的驱动电压下， 两种有机电致发光器件的电压 -电流密度、 电压-亮度曲线 图。 图 5示出了不同电流密度下， 两种有机电致发光器件的电流效率-电流密 度曲线图。 从图 4和图 5中可以看出， 采用由掺杂有 ZnPc的 Bphen制成的 电子传输层的有机电致发光器件的发光性能也要比采用由 Bphen制成的电子 传输层的有机电致发光器件有了很大的提升。
实验结果显示，其他的酞菁类染料掺杂进入 Bphen制成的电子传输层之 后， 包含该电子传输层的有机电致发光器件的电子传输率同样会得到^艮大的 提高。 所述酞菁类染料包括 CuPc、 ZnPc, F16CuPc、 CoPc、 F16CoPc、 TiCl2Pc 和 TiOPc中的一种或多种。
在上文中， 以 Bphen为电子传输层的主体材料为例说明了电子传输层掺 杂酞菁类染料之后电流效率得到很大的提高， 其光电性能和发光效率得到改 善。 本领域技术人员可以理解的是， 当酞菁类染料掺杂进入以其他材料为主 体材料的电子传输层中时， 包含该电子传输层的有机电致发光器件的电子传 输率同样会得到很大的提高。 可以作为电子传输层的主体材料包括 Bphen、 NBphen ( 2,9-bis(naphthalen-2-yl)-4,7-diphenyl- 1 , 10-phenanthroline ) 和 TPBi ( 2,2',2"-( 1 ,3,5-benzinetriyl)-tris( 1 -phenyl- 1 -Hbenzimidazole) ) 中的一种 或多种。
本发明的实施例所提供的有机电致发光器件还可以采用串联叠层式结 构。 串联叠层式有机电致发光器件共用阳极和阴极， 将多个器件串联起来， 这样可以提高有机电致发光器件的发光效率， 延长器件的寿命。
本发明实施例还提供了一种显示装置， 所述显示装置包括上述的有机电 致发光器件， 所述显示装置可以为 OLED显示器、 OLED显示面板、 数码相 机、 手机、 平板电脑或电子纸等具有显示功能的产品或者部件。
以上所述仅是本发明的示范性实施方式， 而非用于限制本发明的保护范 围， 本发明的保护范围由所附的权利要求确定。

Claims

权利要求书
1. 一种有机电致发光器件， 包括阳极、 阴极以及设置在所述阳极和阴极 之间的发光层； 其中， 所述有机电致发光器件还包括：
设置在所述阴极与所述发光层之间的电子传输层， 所述电子传输层中掺 杂有酞菁类染料。
2. 根据权利要求 1所述的有机电致发光器件， 其中， 所述酞菁类染料掺 杂在电子传输层中的质量百分比浓度为大于 0%并小于等于 70%。
3. 根据权利要求 2所述的有机电致发光器件， 其中， 所述酞菁类染料掺 杂在电子传输层中的质量百分比浓度大于等于 40%并小于等于 60%。
4. 根据权利要求 1至 3中任意一项所述的有机电致发光器件， 其中， 所 述酞菁类染料包括 CuPc、 ZnPc、 F16CuPc、 CoPc、 F16CoPc、 TiCl2Pc和 TiOPc 中的一种或多种。
5. 根据权利要求 1至 4中任意一项所述的有机电致发光器件， 其中， 所 述电子传输层的主体材料包括 Bphen、 NBphen和 TPBi中的一种或多种。
6. 根据权利要求 1至 5中任意一项所述的有机电致发光器件， 其中， 所 述阳极为氧化铟锡 ITO图案层。
7. 根据权利要求 1至 6中任意一项所述的有机电致发光器件， 还包括： 设置在所述阳极与所述发光层之间的空穴传输层； 设置在所述阳极与所 述空穴传输层之间的空穴注入层， 设置在所述电子传输层与所述阴极之间的 电子注入层。
8. 根据权利要求 1至 7中任意一项所述的有机电致发光器件， 其中， 所 述有机电致发光器件为串联叠层式结构。
9. 一种显示装置， 包括权利要求 1至 8中任意一项所述的有机电致发光 器件。
PCT/CN2013/087147 2013-05-21 2013-11-14 一种有机电致发光器件及显示装置 Ceased WO2014187084A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/361,056 US20150108444A1 (en) 2013-05-21 2013-11-14 Organic electroluminescence device and display apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310190495.4 2013-05-21
CN2013101904954A CN103346270A (zh) 2013-05-21 2013-05-21 一种有机电致发光器件及显示装置

Publications (1)

Publication Number Publication Date
WO2014187084A1 true WO2014187084A1 (zh) 2014-11-27

Family

ID=49281054

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/087147 Ceased WO2014187084A1 (zh) 2013-05-21 2013-11-14 一种有机电致发光器件及显示装置

Country Status (3)

Country Link
US (1) US20150108444A1 (zh)
CN (1) CN103346270A (zh)
WO (1) WO2014187084A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103346270A (zh) * 2013-05-21 2013-10-09 京东方科技集团股份有限公司 一种有机电致发光器件及显示装置
CN103500802A (zh) * 2013-10-12 2014-01-08 京东方科技集团股份有限公司 有机电致发光器件
CN105185916A (zh) * 2015-07-14 2015-12-23 京东方科技集团股份有限公司 有机电致发光器件及其制作方法、显示装置
JP6815294B2 (ja) * 2016-09-30 2021-01-20 株式会社Ｊｏｌｅｄ 有機ｅｌ素子、および有機ｅｌパネル
MD4535C1 (ro) * 2016-11-24 2018-06-30 Государственный Университет Молд0 Procedeu de obţinere a diodei Schottky pe bază de ZnPc
CN112713213B (zh) * 2020-12-30 2022-07-12 Tcl华星光电技术有限公司 光敏元件及其制备方法、显示装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000340364A (ja) * 1999-05-25 2000-12-08 Tdk Corp 有機ｅｌ素子
CN1786010A (zh) * 2005-10-14 2006-06-14 清华大学 一种二芳烯化合物及其制备方法与应用
CN103346270A (zh) * 2013-05-21 2013-10-09 京东方科技集团股份有限公司 一种有机电致发光器件及显示装置
CN103456895A (zh) * 2012-05-30 2013-12-18 海洋王照明科技股份有限公司 有机电致发光器件及其制备方法
CN103500802A (zh) * 2013-10-12 2014-01-08 京东方科技集团股份有限公司 有机电致发光器件

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7061011B2 (en) * 2003-11-26 2006-06-13 The Trustees Of Princeton University Bipolar organic devices
KR100672535B1 (ko) * 2005-07-25 2007-01-24 엘지전자 주식회사 유기 ｅｌ 소자 및 그 제조방법
US20080061030A1 (en) * 2006-09-13 2008-03-13 Taiwan Semiconductor Manufacturing Co., Ltd. Methods for patterning indium tin oxide films
CN101842917B (zh) * 2007-10-31 2012-10-03 巴斯夫欧洲公司 卤化酞菁的用途
KR20100138939A (ko) * 2008-03-18 2010-12-31 아사히 가라스 가부시키가이샤 전자 디바이스용 기판, 유기 ｌｅｄ 소자용 적층체 및 그의 제조 방법, 유기 ｌｅｄ 소자 및 그의 제조 방법
EP2366753B1 (en) * 2010-03-02 2015-06-17 Semiconductor Energy Laboratory Co., Ltd. Light-Emitting Element and Lighting Device
KR101933952B1 (ko) * 2011-07-01 2018-12-31 가부시키가이샤 한도오따이 에네루기 켄큐쇼 발광 장치, 전자 기기 및 조명 장치
CN102522323A (zh) * 2011-12-28 2012-06-27 华南理工大学 一种ito图案化方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000340364A (ja) * 1999-05-25 2000-12-08 Tdk Corp 有機ｅｌ素子
CN1786010A (zh) * 2005-10-14 2006-06-14 清华大学 一种二芳烯化合物及其制备方法与应用
CN103456895A (zh) * 2012-05-30 2013-12-18 海洋王照明科技股份有限公司 有机电致发光器件及其制备方法
CN103346270A (zh) * 2013-05-21 2013-10-09 京东方科技集团股份有限公司 一种有机电致发光器件及显示装置
CN103500802A (zh) * 2013-10-12 2014-01-08 京东方科技集团股份有限公司 有机电致发光器件

Also Published As

Publication number Publication date
CN103346270A (zh) 2013-10-09
US20150108444A1 (en) 2015-04-23

Similar Documents

Publication Publication Date Title
CN108807481B (zh) 一种有机发光显示面板及显示装置
TWI673894B (zh) 有機電致發光器件
CN104253235B (zh) 有机发光器件
CN112117388B (zh) 有机电致发光器件、显示面板及显示装置
CN108232025B (zh) 一种有机电致发光器件
CN104241540A (zh) 一种有机电致发光显示器件、其制作方法及显示装置
CN111554821B (zh) 有机电致发光器件、显示面板及显示装置
CN102931355B (zh) Oled器件
CN102751449A (zh) 一种有机发光二极管
CN102569660A (zh) 一种叠层结构有机电致发光器件
CN105355797B (zh) 倒置型有机电致发光器件及其制备方法
CN103346270A (zh) 一种有机电致发光器件及显示装置
KR101686718B1 (ko) 유기 발광 장치 및 디스플레이 장치
CN106654033A (zh) 一种有机发光显示面板以及电子设备
CN104321896B (zh) 堆叠式有机发光二极管
TWI650402B (zh) 有機電致發光裝置
WO2022062700A1 (zh) 有机电致发光器件、显示面板及显示装置
CN104134753A (zh) 一种叠层有机电致发光器件
Wang et al. Highly efficient green TADF organic light-emitting diodes by simultaneously manipulating hole and electron transport
WO2015192591A1 (zh) 一种有机电致发光器件、有机电致发光显示装置
CN111200077A (zh) 一种内部光提取结构及包括其的有机发光器件及其制造方法
CN101867021A (zh) 一种蓝色磷光有机电致发光器件及其制备方法
Vasilopoulou et al. Flexible organic light emitting diodes (OLEDs) based on a blue emitting polyfluorene
CN111200078A (zh) 用于有机发光器件的光提取结构及包括其的有机发光器件
CN107611275A (zh) 一种白色发光器件，其显示装置及其制作方法

Legal Events

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

Ref document number: 14361056

Country of ref document: US

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

Ref document number: 13885196

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 27-01-2016)

122 Ep: pct application non-entry in european phase

Ref document number: 13885196

Country of ref document: EP

Kind code of ref document: A1