WO2016033882A1 - 一种有机电致发光显示器件、其制作方法及显示装置 - Google Patents

一种有机电致发光显示器件、其制作方法及显示装置 Download PDF

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WO2016033882A1
WO2016033882A1 PCT/CN2014/092670 CN2014092670W WO2016033882A1 WO 2016033882 A1 WO2016033882 A1 WO 2016033882A1 CN 2014092670 W CN2014092670 W CN 2014092670W WO 2016033882 A1 WO2016033882 A1 WO 2016033882A1
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layer
hole transport
transport layer
display device
hole
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French (fr)
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张金中
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BOE Technology Group Co Ltd
Ordos Yuansheng Optoelectronics Co Ltd
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BOE Technology Group Co Ltd
Ordos Yuansheng Optoelectronics Co Ltd
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Priority to US14/768,851 priority Critical patent/US20160248030A1/en
Priority to EP14892231.3A priority patent/EP3190639A4/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • 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
    • H10K2101/80—Composition varying spatially, e.g. having a spatial gradient
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

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  • the present invention relates to the field of display technologies, and in particular, to an organic electroluminescence display device, a method for fabricating the same, and a display device.
  • OLEDs organic electroluminescence display devices
  • the basic structure of the OLED includes: an anode 01, a hole injection layer 02, a hole transport layer 03, an electron blocking layer 04, a light-emitting layer 05, a hole blocking layer 06, and an electron transport layer 07, which are sequentially disposed.
  • the energy levels of the respective materials are not tilted, and the energy level structure is schematically shown in FIG. 2.
  • a voltage is applied between the anode 01 and the cathode 09 of the OLED to form a current, the electrons in the cathode 09 pass through.
  • the electron injection layer 08, the electron transport layer 07, and the hole blocking layer 06 are transported, and the holes in the anode 01 are transported through the hole injection layer 02, the hole transport layer 03, and the electron blocking layer 04, after which electrons and holes are illuminated.
  • the layer 05 is composited to form an electron-hole pair, and the material in the luminescent layer 05 is excited to emit light. This process causes a tilting of the energy level of each material due to a voltage applied between the cathode 09 and the anode 01. Shown.
  • an embodiment of the present invention provides an organic electroluminescence display device, a manufacturing method thereof, and a display device, which can increase the number of free hole carriers in a hole transport layer and improve the mobility of hole carriers. , thereby improving the luminescent properties of the OLED.
  • an embodiment of the present invention provides an organic electroluminescence display device comprising: a substrate substrate, a hole injection layer, a hole transport layer, and an electron blocking layer disposed on the substrate substrate in sequence, the space
  • the material of the hole transport layer is a material having a P-type doping.
  • the doping concentration of the P-type doping changes in a gradient, so that the energy level of the hole transport layer is Gradient change; among them,
  • the doping concentration of the P-type doping near the hole injection layer is higher than the doping concentration near the electron blocking layer.
  • the difference between the highest occupied energy level between the hole transport layer and the electron blocking layer is less than that of the undoped The difference between the highest occupied energy level between the hole transport layer and the electron blocking layer.
  • the difference between the highest occupied energy level between the hole injection layer and the hole transport layer is smaller than The difference between the highest occupied energy level between the hole injection layer and the undoped hole transport layer.
  • the minimum doping concentration of the P-type doping is 1%, and the maximum doping of the P-type doping The concentration is 6%.
  • the dopant used in the hole transport layer is a P-type oxidant.
  • the P-type oxidant is any of antimony pentachloride, ferric chloride, iodine, F 4 -TCNQ or TBAHA.
  • the P-type oxidant is any of antimony pentachloride, ferric chloride, iodine, F 4 -TCNQ or TBAHA.
  • the embodiment of the invention further provides a method for fabricating the above-mentioned organic electroluminescent display device provided by the embodiment of the invention, comprising sequentially forming a hole injection layer, a hole transport layer and an electron blocking layer on a substrate, wherein Forming a hole transport layer on the substrate substrate specifically includes:
  • a hole transport layer is formed on the base substrate on which the hole injection layer is formed by co-evaporation of the body and P-type doping in the vapor deposition chamber.
  • the method for fabricating the above-mentioned organic electroluminescent display device provided by the embodiment of the present invention the forming a hole transport layer on the substrate substrate further includes:
  • the concentration of the P-type dopant in the formed hole transport layer is controlled by controlling the temperature at which the P-type doping is evaporated.
  • the embodiment of the invention further provides a display device comprising the above organic electroluminescent display device provided by the embodiment of the invention.
  • An organic electroluminescence display device comprising a substrate substrate, a hole injection layer, a hole transport layer and an electron blocking layer disposed on the substrate substrate, wherein
  • the material of the hole transport layer is a material having a P-type doping
  • the LUMO level of the P-type doping is close to the HOMO level of the bulk material of the hole transport layer, and thus the HOMO level of the bulk material of the hole transport layer is Electrons can transition to the P-type doped LUMO energy level, thereby increasing the number of free hole carriers in the hole transport layer and increasing the mobility of hole carriers, thus facilitating the improvement of electrons and holes in the light-emitting layer.
  • the probability of complexing electron-hole pairs is formed to improve the balance of electron-hole pairs, thereby improving the luminescent properties of the OLED.
  • FIG. 1 is a schematic structural view of an organic electroluminescent display device in the prior art
  • FIG. 2 is a schematic view showing the structure of an energy level of an organic electroluminescent display device in the prior art when no voltage is applied;
  • FIG. 3 is a schematic view showing the structure of an energy level of an organic electroluminescent display device in the prior art when a voltage is applied;
  • FIGS. 4a and 4b are schematic structural views of an organic electroluminescent display device according to an embodiment of the present invention.
  • FIG. 5 is a schematic diagram showing the structure of an energy level of an organic electroluminescence display device according to an embodiment of the present invention when no voltage is applied;
  • FIG. 6 is a schematic diagram showing the structure of an energy level of an organic electroluminescence display device according to an embodiment of the present invention when a voltage is applied.
  • An embodiment of the present invention provides an organic electroluminescence display device, as shown in FIG. 4a, comprising: a substrate substrate 20, a hole injection layer 02, a hole transport layer 03, and an electron sequentially disposed on the base substrate 20.
  • the material of the hole transport layer 03 in the above organic electroluminescent display device provided by the embodiment of the present invention is doped with a P-type material, and the PMO-doped LUMO energy level and the hole transport layer 03 bulk material HOMO
  • the energy levels are relatively close, so that the electrons in the HOMO level of the bulk material of the hole transport layer 03 can transition to the P-type doped LUMO energy level, thereby increasing the number of free hole carriers in the hole transport layer 03, thereby increasing the number of holes.
  • the mobility of hole carriers facilitates the increase of the probability of electrons and holes recombining to form electron-hole pairs in the light-emitting layer to improve the balance of electron-hole pairs, thereby improving the luminescent properties of the OLED.
  • the hole transport can be adjusted by adjusting The concentration of the P-type dopant in layer 03 adjusts the energy level of the hole transport layer 03.
  • the doping concentration of the P-type doping in the hole transport layer 03 may be adjusted to be a gradient change, so that the energy level of the hole transport layer 03 also changes in a gradient; wherein, the P-type doping may be specifically controlled.
  • the doping concentration near the hole injection layer 02 is higher than the doping concentration near the electron blocking layer 04, as shown in FIG. 4a, that is, the concentration of the P-type doping is gradually lowered during the formation of the hole transport layer 03, thus,
  • the highest occupied level of the hole transport layer 03 near the hole injection layer 02 can be made closer to the highest occupied level of the hole injection layer 02, closer to the highest occupied energy level near the electron blocking layer 04.
  • the hole transport layer 03 and the electron blocking can be achieved by adjusting the concentration of the P-type doping near the electron blocking layer 04 in the hole transport layer 03, that is, adjusting the minimum doping concentration of the P-type doping.
  • the difference between the highest occupied energy levels between the layers 04 is smaller than the difference between the highest occupied energy levels between the undoped hole transport layer 03 and the electron blocking layer 04, which can reduce the hole transport layer 03 and the electron blocking layer.
  • the HOMO barrier between 04 improves the hole transport efficiency and enhances the overall luminous efficiency of the OLED device.
  • the concentration of the P-type doping near the hole injection layer 02 in the hole transport layer 03 that is, to adjust the maximum doping concentration of the P-type doping to achieve empty
  • the difference between the highest occupied energy level between the hole transport layer 03 and the hole injection layer 02 is smaller than the difference between the highest occupied energy level between the undoped hole transport layer 03 and the hole injection layer 02, which can be lowered.
  • the HOMO barrier between the hole transport layer 03 and the hole injection layer 02 improves hole transport efficiency and enhances the overall luminous efficiency of the OLED device.
  • the doping concentration of the P-type doping in the hole transport layer 03 can be controlled to achieve the above purpose.
  • the minimum doping concentration of the P-type doping is generally controlled at 1%, and the P-type is preferred.
  • the maximum doping concentration of the doping is generally controlled at 6%.
  • the dopant used in the hole transport layer 03 is generally a P-type oxidant.
  • the P-type oxidant is any one of antimony pentachloride, ferric chloride, iodine, F 4 -TCNQ or TBAHA.
  • the material of the hole transport layer 03 is generally selected from NPB or a biphenyldiamine derivative, and the material of the hole injection layer 02 may be a material such as copper phthalocyanine, PEDT, PSS or TNANA.
  • the light-emitting layer 05, the hole blocking layer 06, and the electrons are sequentially disposed on the electron blocking layer 04.
  • a transport layer 07, an electron injection layer 08, a cathode 09 and a cathode protective layer 10; and a buffer layer, a polysilicon layer, and a gate layer are generally disposed between the base substrate 20 and the hole injection layer 02.
  • the anode 01 may specifically adopt an ITO/Ag/ITO structure, and the thickness thereof may specifically be 500A/100A/500A.
  • the light emitting layer 05 may be composed of a green light emitting layer, a red light emitting layer, and a blue light emitting layer.
  • the above three types of light-emitting layers can be classified into a fluorescent light-emitting layer and a phosphorescent light-emitting layer.
  • the phosphorescence of the red luminescent layer may be a DCJTB-like derivative, a star-shaped DCM derivative, a polycyclic aromatic hydrocarbon or an undoped red fluorescent material containing a D/A framework.
  • Green fluorescent materials include quinacridone derivatives, coumarin derivatives, polycyclic aromatic hydrocarbons.
  • the blue fluorescent material includes a diaryl hydrazine derivative, a stilbene aromatic derivative, an anthracene derivative, a cyclodane fluorenyl derivative, TBP, DSA-Ph, IDE-102 and the like.
  • the phosphorescent host material may be a main illuminant material containing a carbazole group, a main illuminant material having electron transport properties, or the like.
  • the red, green, and blue phosphorescent dopant materials may be Pt complex, Ir complex, Eu complex, Os complex or FIrpic.
  • the material of the hole blocking layer 06 may be BCP.
  • the material of the electron transport layer 07 may be a quinoline derivative, a diazonium derivative, a silicon-containing heterocyclic compound, a porphyrin derivative, a phenanthroline derivative or a perfluorinated oligomer.
  • the material of the electron injecting layer 08 may be an alkali metal oxide such as Li 2 O, LiBO 2 , K 2 SiO 3 , Cs 2 CO 3 , an alkali metal acetate or an alkali metal fluoride.
  • the material of the cathode 09 may be a Li:Al alloy or a Mg:Ag alloy.
  • the above-mentioned organic electroluminescent display device has a specific structure as shown in FIG. 4b.
  • the energy levels of the respective materials are not inclined, and the energy level is The structure is shown in Fig. 5.
  • the energy level of the hole transport layer 03 changes in a gradient, and the number of free hole carriers in the hole transport layer 03 is larger than that in the undoped state;
  • the anode of the doped OLED is When a voltage is applied between 01 and cathode 09 to form a current, the energy levels of the respective materials are tilted, and the energy level structure is shown in FIG. 6.
  • This energy level structure can improve the hole transport relative to the existing energy level structure.
  • the ability to increase the probability of electrons and holes recombining to form electron-hole pairs in the light-emitting layer is advantageous for exciting the material in the light-emitting layer to emit light.
  • an embodiment of the present invention further provides a method for fabricating the above-described organic electroluminescent display device provided by the embodiment of the present invention.
  • the principle of solving the problem is similar to the foregoing organic electroluminescent display device. Therefore, the implementation of the method can be referred to the implementation of the organic electroluminescent display device, and the repeated description will not be repeated.
  • a method for fabricating an organic electroluminescence display device includes sequentially forming a hole injection layer, a hole transport layer, and an electron blocking layer on a substrate, wherein the substrate is formed on the substrate.
  • the hole transport layer specifically includes:
  • a hole transport layer is formed on the base substrate on which the hole injection layer is formed by co-evaporation of the body and P-type doping in the vapor deposition chamber.
  • the method for fabricating the above-mentioned organic electroluminescent display device provided by the embodiment of the present invention the forming a hole transport layer on the substrate substrate further includes:
  • the concentration of the P-type doping in the formed hole transport layer is controlled by controlling the temperature of the vapor-deposited P-type doping so that the P-type doping in the formed hole transport layer changes in a gradient.
  • the method of co-depositing in the vapor deposition chamber by vacuum thermal evaporation Body and P-type doping In the process of forming a hole transport layer on a base substrate on which a hole injection layer is formed, the temperature of the evaporation source can be controlled, and the P-type can be lowered by lowering the temperature of the vapor-deposited P-type doping.
  • the doping evaporation rate which in turn reduces the doping concentration of the P-type doping, causes the doping concentration of the P-type doping to change in a gradient, and also causes the energy level of the hole transport layer to change in a gradient, thereby increasing the hole transport layer.
  • the number of free hole carriers increases the mobility of hole carriers, thereby improving the luminescent properties of the OLED, and preparing a highly efficient OLED device.
  • anode layer on the base substrate is an ITO/Ag/ITO structure, and the thickness is 500 A/100 A/500 A;
  • a hole injecting layer is formed on the substrate substrate on which the anode layer is formed by co-evaporating the body in the vapor deposition chamber, wherein the hole is deposited using a high-precision mask
  • the material of the injection layer and the hole injection layer includes copper phthalocyanine, PEDT, PSS and TNANA materials;
  • a hole transport layer is formed on the base substrate on which the hole injection layer is formed by co-evaporation of the body and P-type doping in the vapor deposition chamber, wherein the hole transport layer is formed.
  • the precision mask layer deposits a hole transport layer, and the material of the hole transport layer includes NPB and a biphenyldiamine derivative, and the P-type doped material may be antimony pentachloride, ferric chloride, iodine, F4-TCNQ or Materials such as TBAHA can also be homemade oxidants;
  • an electron blocking layer is formed on the substrate substrate on which the hole transport layer is formed by co-evaporating the body in the vapor deposition chamber, wherein the electrons are deposited using a high precision mask a barrier layer, the electron blocking layer can block the transmission of electrons without hindering the transport of holes;
  • a light-emitting layer is formed on the base substrate on which the electron blocking layer is formed by vapor-depositing the body in the vapor deposition chamber, wherein the light-emitting layer is deposited by using a high-precision mask
  • the light emitting layer may be a red light emitting layer, a green light emitting layer and a blue light emitting layer.
  • the above three types of light emitting layers may be divided into a fluorescent emitting layer and a phosphorescent emitting layer, wherein the material of the red fluorescent emitting layer comprises a DCJTB-like derivative, a star shape DCM derivatives, polycyclic aromatic hydrocarbons and undoped red fluorescent materials containing D/A framework; materials of green fluorescent emitting layers include quinophthalone derivatives, coumarin derivatives and polycyclic aromatics Group of hydrocarbons; blue fluorescent light emitting layer materials include diaryl fluorene derivatives, stilbene aromatic derivatives, anthracene derivatives, cyclodane fluorenyl derivatives, TBP, DSA-Ph and IDE-102;
  • the phosphorescent host material may be a main illuminant material containing a carbazole group, a main illuminant material having electron transport properties, and the like, and the red, green, and blue phosphorescent dopant materials may be Pt complexes, Ir is misaligned. , Eu complex
  • a hole blocking layer, an electron transport layer, an electron injection layer and a cathode are sequentially formed on the base substrate on which the light emitting layer is formed by co-evaporating the body in the vapor deposition chamber.
  • the material of the hole blocking layer may be BCP
  • the material of the electron transport layer may be a quinoline derivative, a nitrogen hydrazine derivative, a silicon-containing heterocyclic compound, a porphyrin derivative, a phenanthroline derivative or a perfluorinated oligomer
  • the material of the electron injecting layer may be an alkali metal oxide or an alkali metal acetate.
  • the material of the cathode layer may be a Li:Al alloy or a Mg:Ag alloy;
  • a cathode protective layer is sequentially formed on the base substrate on which the cathode layer is formed by co-evaporating the body in the vapor deposition chamber, wherein the cathode protective layer is deposited by using an open mask
  • the cathodic protection layer is used to protect the entire OLED device from corrosion and oxidation.
  • the above-mentioned organic electroluminescent display device provided by the embodiment of the present invention has been produced through the above steps 1 to 7 provided by the examples.
  • an embodiment of the present invention further provides a display device, including the above-mentioned organic electroluminescent display device provided by the embodiment of the present invention, which may be: a mobile phone, a tablet computer, a television, a display, a notebook computer. , digital photo frame, navigator, etc. Any product or component with display function.
  • a display device including the above-mentioned organic electroluminescent display device provided by the embodiment of the present invention, which may be: a mobile phone, a tablet computer, a television, a display, a notebook computer. , digital photo frame, navigator, etc. Any product or component with display function.
  • Other indispensable components of the display device are understood by those skilled in the art, and are not described herein, nor should they be construed as limiting the invention.
  • An organic electroluminescence display device comprising a substrate substrate, a hole injection layer, a hole transport layer and an electron blocking layer disposed on the substrate substrate, wherein
  • the material of the hole transport layer is a material having a P-type doping
  • the LUMO level of the P-type doping is close to the HOMO level of the bulk material of the hole transport layer, and thus the HOMO level of the bulk material of the hole transport layer is Electrons can transition to the P-type doped LUMO energy level, thereby increasing the number of free hole carriers in the hole transport layer and increasing the mobility of hole carriers, thus facilitating the improvement of electrons and holes in the light-emitting layer.

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Abstract

一种有机电致发光显示器件、其制作方法及显示装置，包括衬底基板（20），依次设置在衬底基板（20）上的空穴注入层（02）、空穴传输层（03）和电子阻挡层（04），其中，空穴传输层（03）的材料为具有P型掺杂的材料，P型掺杂的LUMO能级与空穴传输层（03）本体材料的HOMO能级较为接近，因此空穴传输层（03）本体材料的HOMO能级中电子能够跃迁到P型掺杂的LUMO能级，从而增加空穴传输层（03）中自由空穴载流子的数量，提高了空穴载流子的迁移率，这样便于提高电子和空穴在发光层复合形成电子-空穴对的几率，以改善电子-空穴对的平衡程度，从而提高OLED的发光性能。

Description

一种有机电致发光显示器件、其制作方法及显示装置 技术领域
本发明涉及显示技术领域，尤其涉及一种有机电致发光显示器件、其制作方法及显示装置。
背景技术
目前，有机电致发光显示器件(Organic Electroluminesecent Display，OLED)凭借其低功耗、高色饱和度、广视角、薄厚度、能实现柔性化等优异性能，已经逐渐成为显示领域的主流。
OLED的基本结构，如图1所示，包括：依次设置的阳极01，空穴注入层02，空穴传输层03，电子阻挡层04，发光层05，空穴阻挡层06，电子传输层07，电子注入层08，阴极09和阴极保护层10。当OLED没有施加电压时，各个材料的能级未发生倾斜，能级结构示意图如图2所示；当OLED的阳极01和阴极09之间施加了电压以形成电流时，阴极09中的电子经过电子注入层08、电子传输层07和空穴阻挡层06传输，而阳极01中的空穴经过空穴注入层02、空穴传输层03和电子阻挡层04传输，之后电子和空穴在发光层05复合形成电子-空穴对，激发发光层05中的材料进行发光，这个过程由于在阴极09和阳极01之间施加了电压使得各个材料的能级发生倾斜，能级结构示意图如图3所示。
由于采用现有技术形成的空穴传输层03与电子阻挡层04之间的最高已占有能级(Highest Occupied Molecular Oribital，HOMO)之差比较大，这使得空穴不容易越过空穴传输层03与电子阻挡层04之间的势垒；同时，空穴注入层02与空穴传输层03之间比较大的HOMO之差也妨碍了空穴的传输，使得空穴传输效率降低，导致OLED器件的发光效率不高。
发明内容
有鉴于此，本发明实施例提供一种有机电致发光显示器件、其制作方法及显示装置，可以增加空穴传输层中自由空穴载流子的数量，提高空穴载流子的迁移率，从而提高OLED的发光性能。
因此，本发明实施例提供了一种有机电致发光显示器件，包括：衬底基板，依次设置在所述衬底基板上的空穴注入层、空穴传输层和电子阻挡层，所述空穴传输层的材料为具有P型掺杂的材料。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述P型掺杂的掺杂浓度呈梯度变化，使所述空穴传输层的能级呈梯度变化；其中，
所述P型掺杂靠近所述空穴注入层的掺杂浓度高于靠近所述电子阻挡层的掺杂浓度。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述空穴传输层与所述电子阻挡层之间的最高已占有能级之差小于未掺杂的所述空穴传输层与所述电子阻挡层之间的最高已占有能级之差。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述空穴注入层与所述空穴传输层之间的最高已占有能级之差小于所述空穴注入层与未掺杂的所述空穴传输层之间的最高已占有能级之差。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述P型掺杂的最小掺杂浓度为1％，所述P型掺杂的最大掺杂浓度为6％。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述空穴传输层采用的掺杂剂为P型氧化剂。
在一种可能的实现方式中，在本发明实施例提供的上述有机电致发光显示器件中，所述P型氧化剂为五氯化锑，氯化铁，碘，F4-TCNQ或TBAHA中任意一种。
本发明实施例还提供了一种本发明实施例提供的上述有机电致发光显示器件的制作方法，包括在衬底基板上依次形成空穴注入层、空穴传输层和电子阻挡层，其中在所述衬底基板上形成空穴传输层具体包括：
在蒸镀腔内通过共同蒸镀本体和P型掺杂的方式，在形成有空穴注入层的衬底基板上形成空穴传输层。
在一种可能的实现方式中，本发明实施例提供的上述有机电致发光显示器件的制作方法，在所述衬底基板上形成空穴传输层还包括：
通过控制蒸镀所述P型掺杂的温度，控制形成的空穴传输层中P型掺杂的浓度。
本发明实施例还提供了一种显示装置，包括本发明实施例提供的上述有机电致发光显示器件。
本发明有益效果如下：
本发明实施例提供的一种有机电致发光显示器件、其制作方法及显示装置，包括衬底基板，依次设置在衬底基板上的空穴注入层、空穴传输层和电子阻挡层，其中，空穴传输层的材料为具有P型掺杂的材料，P型掺杂的LUMO能级与空穴传输层本体材料的HOMO能级较为接近，因此空穴传输层本体材料的HOMO能级中电子能够跃迁到P型掺杂的LUMO能级，从而增加空穴传输层中自由空穴载流子的数量，提高了空穴载流子的迁移率，这样便于提高电子和空穴在发光层复合形成电子-空穴对的几率，以改善电子-空穴对的平衡程度，从而提高OLED的发光性能。
附图说明
图1为现有技术中有机电致发光显示器件的结构示意图；
图2为现有技术中有机电致发光显示器件在未施加电压时的能级结构示意图；
图3为现有技术中有机电致发光显示器件在施加电压时的能级结构示意图；
图4a和图4b分别为本发明实施例提供的有机电致发光显示器件的结构示意图；
图5为本发明实施例提供的有机电致发光显示器件在未施加电压时的能级结构示意图；
图6为本发明实施例提供的有机电致发光显示器件在施加电压时的能级结构示意图。
具体实施方式
下面结合附图，对本发明实施例提供的有机电致发光显示器件、其制作方法及显示装置的具体实施方式进行详细地说明。
其中，附图中各膜层的厚度和形状不反映有机电致发光显示器件 的真实比例，目的只是示意说明本发明内容。
本发明实施例提供了一种有机电致发光显示器件，如图4a所示，包括：衬底基板20，依次设置在衬底基板20上的空穴注入层02、空穴传输层03和电子阻挡层04；其中，空穴传输层03的材料为具有P型掺杂的材料。
由于本发明实施例提供的上述有机电致发光显示器件中的空穴传输层03的材料中掺杂了P型材料，而P型掺杂的LUMO能级与空穴传输层03本体材料的HOMO能级较为接近，因此空穴传输层03本体材料的HOMO能级中电子能够跃迁到P型掺杂的LUMO能级，从而增加空穴传输层03中自由空穴载流子的数量，提高了空穴载流子的迁移率，这样便于提高电子和空穴在发光层复合形成电子-空穴对的几率，以改善电子-空穴对的平衡程度，从而提高OLED的发光性能。
具体地，在本发明实施例提供的上述有机电致发光显示器件中，由于随着P型掺杂浓度的改变，空穴传输层03能级也随之改变，因此，可以通过调整空穴传输层03中P型掺杂的浓度来调整空穴传输层03的能级。
在具体实施时，可以调整空穴传输层03中的P型掺杂的掺杂浓度呈梯度变化，以使空穴传输层03的能级也呈梯度变化；其中，具体可以控制P型掺杂靠近空穴注入层02的掺杂浓度高于靠近电子阻挡层04的掺杂浓度，如图4a所示，即在形成空穴传输层03的过程中逐渐降低P型掺杂的浓度，这样，可以使得空穴传输层03在靠近空穴注入层02处的最高已占有能级更接近空穴注入层02的最高已占有能级，在靠近电子阻挡层04处的最高已占有能级更接近电子阻挡层04的最高已占有能级。
在具体实施时，可以通过调整空穴传输层03中靠近电子阻挡层04处的P型掺杂的浓度，即调整P型掺杂的最小掺杂浓度，以达到空穴传输层03与电子阻挡层04之间的最高已占有能级之差小于未掺杂的空穴传输层03与电子阻挡层04之间的最高已占有能级之差，这样可以降低空穴传输层03和电子阻挡层04之间的HOMO势垒，提高空穴传输效率，增强OLED器件整体的发光效率。
在具体实施时，还可以通过调整空穴传输层03中靠近空穴注入层02处的P型掺杂的浓度，即调整P型掺杂的最大掺杂浓度，以达到空 穴传输层03与空穴注入层02之间的最高已占有能级之差小于未掺杂的空穴传输层03与空穴注入层02之间的最高已占有能级之差，这样可以降低空穴传输层03和空穴注入层02之间的HOMO势垒，提高空穴传输效率，增强OLED器件整体的发光效率。
在具体实施时，可以控制空穴传输层03中的P型掺杂的掺杂浓度，以达到上述目的，具体地，P型掺杂的最小掺杂浓度一般控制在1％为佳，P型掺杂的最大掺杂浓度一般控制在6％为佳。
在具体实施时，在本发明实施例提供的上述有机电致发光显示器件中，空穴传输层03一般采用的掺杂剂为P型氧化剂。
一般地，在具体实施时，在本发明实施例提供的上述有机电致发光显示器件中，P型氧化剂为五氯化锑，氯化铁，碘，F4-TCNQ或TBAHA中任意一种。
在具体实施时，空穴传输层03的材料一般选取NPB或联苯二胺衍生物等，空穴注入层02的材料可以为铜酞菁、PEDT、PSS或TNANA等材料。
在具体实施时，在本发明实施例提供的上述有机电致发光显示器件中，如图4b所示，一般还包括依次设置在电子阻挡层04上的发光层05，空穴阻挡层06，电子传输层07，电子注入层08，阴极09和阴极保护层10等膜层；并且，在衬底基板20和空穴注入层02之间一般还会设置有缓冲层，多晶硅层，栅极层，栅极绝缘层，ILD层，SD层，PVX层，有机树脂PLN层，阳极01，像素限定层(PDL层)等膜层，图4b中仅示出了阳极01。
具体地，阳极01可以具体采用ITO/Ag/ITO结构，其厚度可以具体采用500A/100A/500A。
具体地，发光层05可以由绿光发光层，红光发光层和蓝光发光层组成。以上三类发光层可以分为荧光发光层和磷光发光层。红色发光层的磷光可以为类DCJTB衍生物，星状DCM衍生物，多环芳香族碳氢化合物或含D/A架构的非掺杂型红光荧光材料。绿色荧光材料包括喹吖叮酮衍生物，香豆素衍生物，多环芳香族碳氢化合物。蓝色荧光材料包括二芳香基蒽衍生物，二苯乙烯芳香族衍生物，芘衍生物，旋环双芴基衍生物，TBP,DSA-Ph,IDE-102等。磷光发光主体材料可以为含咔唑基团的主发光体材料,具有电子传输性质的主发光体材料等。而 红色、绿色、蓝色的磷光掺杂材料可以为Pt错合物，Ir错合物，Eu错合物，Os错合物或FIrpic等。
具体地，空穴阻挡层06材料可以为BCP。
具体地，电子传输层07的材料可以为喹啉衍生物，二氮蒽衍生物，含硅的杂环化合物，喔啉衍生物，二氮菲衍生物或全氟化寡聚物。
具体地，电子注入层08的材料可以为碱金属氧化物例如Li2O，LiBO2，K2SiO3，Cs2CO3，也可以为碱金属醋酸盐，也可以为碱金属氟化物。
具体地，阴极09的材料可以为Li:Al合金或者Mg:Ag合金。
具体地，本发明实施例提供的上述有机电致发光显示器件如图4b所示的具体结构，当在阳极01和阴极09之间没有施加电压时，各个材料的能级未发生倾斜，能级结构示意图如图5所示，此时空穴传输层03的能级呈梯度变化，空穴传输层03中自由空穴载流子的数量比未掺杂时的多；当掺杂的OLED的阳极01和阴极09之间施加了电压以形成电流时，各个材料的能级发生倾斜，能级结构示意图如图6所示，此能级结构相对于现有的能级结构能提高空穴的传输能力，这样便于提高电子和空穴在发光层复合形成电子-空穴对的几率，有利于激发发光层中的材料进行发光。
基于同一发明构思，本发明实施例还提供了一种本发明实施例提供的上述有机电致发光显示器件的制作方法，由于该方法解决问题的原理与前述一种有机电致发光显示器件相似，因此该方法的实施可以参见有机电致发光显示器件的实施，重复之处不再赘述。
在具体实施时，本发明实施例提供的有机电致发光显示器件的制作方法，包括在衬底基板上依次形成空穴注入层、空穴传输层和电子阻挡层，其中在衬底基板上形成空穴传输层具体包括：
在蒸镀腔内通过共同蒸镀本体和P型掺杂的方式，在形成有空穴注入层的衬底基板上形成空穴传输层。
进一步地，在具体实施时，本发明实施例提供的上述有机电致发光显示器件的制作方法，在衬底基板上形成空穴传输层还包括：
通过控制蒸镀P型掺杂的温度，控制形成的空穴传输层中P型掺杂的浓度，以便在形成的空穴传输层中的P型掺杂呈梯度变化。
在具体实施时，通过真空热蒸镀的方法，在蒸镀腔内共同蒸镀本 体和P型掺杂在形成有空穴注入层的衬底基板上形成空穴传输层的过程中，蒸发源的温度可以进行控制，通过降低蒸镀P型掺杂的温度，可以降低P型掺杂的蒸发速率，进而降低P型掺杂的掺杂浓度，使P型掺杂的掺杂浓度呈梯度变化，也使空穴传输层的能级呈梯度变化，这样可以增加空穴传输层中自由空穴载流子的数量，提高空穴载流子的迁移率，从而提高OLED的发光性能，制备出高效率的OLED器件。
下面以一个具体的实例详细地说明本发明实施例提供的有机电致发光显示器件的制作方法，具体步骤如下：
1、在衬底基板上形成阳极层，所形成的阳极层为ITO/Ag/ITO结构，厚度为500A/100A/500A；
2、在高真空蒸镀腔体中，在蒸镀腔内通过共同蒸镀本体的方式，在形成有阳极层的衬底基板上形成空穴注入层，其中利用高精度掩膜板沉积空穴注入层，空穴注入层的材料包括铜酞菁，PEDT，PSS和TNANA材料；
3、在高真空蒸镀腔体中，在蒸镀腔内通过共同蒸镀本体和P型掺杂的方式，在形成有空穴注入层的衬底基板上形成空穴传输层，其中利用高精度掩膜板沉积空穴传输层，空穴传输层的材料包括NPB和联苯二胺衍生物，同时P型掺杂的材料可以为五氯化锑，氯化铁，碘，F4-TCNQ或TBAHA等材料，也可以是自制的氧化剂；
4、在高真空蒸镀腔体中，在蒸镀腔内通过共同蒸镀本体的方式，在形成有空穴传输层的衬底基板上形成电子阻挡层，其中利用高精度掩膜板沉积电子阻挡层，电子阻挡层可以阻挡电子的传送，而不阻碍空穴的传输；
5、在下一个高真空蒸镀腔体中，在蒸镀腔内通过分别蒸镀本体的方式，在形成有电子阻挡层的衬底基板上形成发光层，其中利用高精度掩膜板沉积发光层，发光层可以是红光发光层，绿光发光层和蓝光发光层，以上三类发光层可以分为荧光发光层和磷光发光层，其中红色荧光发光层的材料包括类DCJTB衍生物，星状DCM衍生物，多环芳香族碳氢化合物和含D/A架构的非掺杂型红光荧光材料；绿色荧光发光层的材料包括喹吖叮酮衍生物，香豆素衍生物和多环芳香族碳氢化合物；蓝色荧光发光层的材料包括二芳香基蒽衍生物，二苯乙烯芳香族衍生物、芘衍生物，旋环双芴基衍生物，TBP，DSA-Ph和IDE-102； 磷光发光主体材料可以为含咔唑基团的主发光体材料，具有电子传输性质的主发光体材料等，而红色、绿色、蓝色的磷光掺杂材料可以为Pt错合物，Ir错合物，Eu错合物，Os错合物或FIrpic等；
6、在高真空蒸镀腔体中，在蒸镀腔内通过共同蒸镀本体的方式，在形成有发光层的衬底基板上依次形成空穴阻挡层，电子传输层，电子注入层和阴极层，其中利用高精度掩膜板依次沉积空穴阻挡层，电子传输层，电子注入层和阴极层，空穴阻挡层的材料可以为BCP，电子传输层的材料可以为喹啉衍生物，二氮蒽衍生物，含硅的杂环化合物，喔啉衍生物，二氮菲衍生物或全氟化寡聚物，电子注入层的材料可以为碱金属氧化物，也可以为碱金属醋酸盐，也可以为碱金属氟化物，阴极层的材料可以为Li:Al合金或者Mg:Ag合金；
7、在高真空蒸镀腔体中，在蒸镀腔内通过共同蒸镀本体的方式，在形成有阴极层的衬底基板上依次形成阴极保护层，其中利用开放掩膜板沉积阴极保护层，阴极保护层是用来保护整个OLED器件避免受到腐蚀和氧化。
至此，经过实例提供的上述步骤1至7制作出了本发明实施例提供的上述有机电致发光显示器件。
基于同一发明构思，本发明实施例还提供了一种显示装置，包括本发明实施例提供的上述有机电致发光显示器件，该显示装置可以为：手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。对于该显示装置的其它必不可少的组成部分均为本领域的普通技术人员应该理解具有的，在此不做赘述，也不应作为对本发明的限制。该显示装置的实施可以参见上述有机电致发光显示器件的实施例，重复之处不再赘述。
本发明实施例提供的一种有机电致发光显示器件、其制作方法及显示装置，包括衬底基板，依次设置在衬底基板上的空穴注入层、空穴传输层和电子阻挡层，其中，空穴传输层的材料为具有P型掺杂的材料，P型掺杂的LUMO能级与空穴传输层本体材料的HOMO能级较为接近，因此空穴传输层本体材料的HOMO能级中电子能够跃迁到P型掺杂的LUMO能级，从而增加空穴传输层中自由空穴载流子的数量，提高了空穴载流子的迁移率，这样便于提高电子和空穴在发光层复合形成电子-空穴对的几率，以改善电子-空穴对的平衡程度，从而提高 OLED的发光性能。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (10)

  1. 一种有机电致发光显示器件，包括：衬底基板，依次设置在所述衬底基板上的空穴注入层、空穴传输层和电子阻挡层，其特征在于：
    所述空穴传输层的材料为具有P型掺杂的材料。
  2. 如权利要求1所述的有机电致发光显示器件，所述P型掺杂的掺杂浓度呈梯度变化，使所述空穴传输层的能级呈梯度变化；其中，
    所述P型掺杂靠近所述空穴注入层的掺杂浓度高于靠近所述电子阻挡层的掺杂浓度。
  3. 如权利要求2所述的有机电致发光显示器件，其特征在于，所述空穴传输层与所述电子阻挡层之间的最高已占有能级之差小于未掺杂的所述空穴传输层与所述电子阻挡层之间的最高已占有能级之差。
  4. 如权利要求2所述的有机电致发光显示器件，其特征在于，所述空穴注入层与所述空穴传输层之间的最高已占有能级之差小于所述空穴注入层与未掺杂的所述空穴传输层之间的最高已占有能级之差。
  5. 如权利要求2所述的有机电致发光显示器件，其特征在于，所述P型掺杂的最小掺杂浓度为1％，所述P型掺杂的最大掺杂浓度为6％。
  6. 如权利要求5所述的有机电致发光显示器件，其特征在于，所述空穴传输层采用的掺杂剂为P型氧化剂。
  7. 如权利要求6所述的有机电致发光显示器件，其特征在于，所述P型氧化剂为五氯化锑，氯化铁，碘，F4-TCNQ或TBAHA中任意一种。
  8. 一种如权利要求1-7任一项所述有机电致发光显示器件的制作方法，包括在衬底基板上依次形成空穴注入层、空穴传输层和电子阻挡层，其特征在于，其中在所述衬底基板上形成空穴传输层具体包括：
    在蒸镀腔内通过共同蒸镀本体和P型掺杂的方式，在形成有空穴注入层的衬底基板上形成空穴传输层。
  9. 如权利要求8所述的制作方法，其特征在于，在所述衬底基板上形成空穴传输层还包括：
    通过控制蒸镀所述P型掺杂的温度，控制形成的空穴传输层中P型掺杂的浓度。
  10. 一种显示装置，其特征在于，包括如权利要求1-7任一项所述的有机电致发光显示器件。
PCT/CN2014/092670 2014-09-04 2014-12-01 一种有机电致发光显示器件、其制作方法及显示装置 Ceased WO2016033882A1 (zh)

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