WO2020113574A1 - Dispositif oled et son procédé de préparation, et solution de matière première pour formation de film de revêtement par centrifugation - Google Patents

Dispositif oled et son procédé de préparation, et solution de matière première pour formation de film de revêtement par centrifugation Download PDF

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Publication number
WO2020113574A1
WO2020113574A1 PCT/CN2018/119893 CN2018119893W WO2020113574A1 WO 2020113574 A1 WO2020113574 A1 WO 2020113574A1 CN 2018119893 W CN2018119893 W CN 2018119893W WO 2020113574 A1 WO2020113574 A1 WO 2020113574A1
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WO
WIPO (PCT)
Prior art keywords
oled device
methyl benzoate
raw material
toluene
transport layer
Prior art date
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Ceased
Application number
PCT/CN2018/119893
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English (en)
Chinese (zh)
Inventor
闵超
李灵芝
王超
赖瑞云
舒鹏
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.)
Shenzhen Royole Technologies Co Ltd
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Shenzhen Royole Technologies Co Ltd
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Application filed by Shenzhen Royole Technologies Co Ltd filed Critical Shenzhen Royole Technologies Co Ltd
Priority to PCT/CN2018/119893 priority Critical patent/WO2020113574A1/fr
Priority to CN201880095919.XA priority patent/CN112640151A/zh
Publication of WO2020113574A1 publication Critical patent/WO2020113574A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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

Definitions

  • the present application relates to the field of display technology, and in particular, to an OLED device and a method for preparing the same, and a raw material solution formed by spin coating.
  • Organic electroluminescent devices (Organic Light-Emitting Diode, OLED) are self-luminous devices, which attract people's extensive attention due to their thin body, large area, and flexibility, and have important applications in the field of display and lighting.
  • a typical OLED device has an anode, an organic functional layer, and a cathode that are sequentially formed on the substrate.
  • the organic functional layer of the OLED device may have different structures, for example, the organic functional layer includes a hole transport layer for hole injection and transport. The preparation process of the hole transport layer greatly affects the performance and long-term stability of the OLED device.
  • the inventor found that although the hole transport layer is prepared using traditional materials and spin coating, although the process is simple and the manufacturing cost is low, the resulting OLED device has low current efficiency and poor OLED device performance.
  • the present application aims to provide a preparation method of an OLED device, an OLED device, and a raw material solution formed by spin coating to solve the technical problems of low current efficiency and poor device performance of an OLED device obtained by a traditional preparation process.
  • a technical solution adopted in the embodiments of the present application is to provide a method for preparing an OLED device, including: preparing a raw material solution, the solute of the raw material solution is TAPC, and methyl benzoate is added to the solvent Spin coating the raw material solution and drying the solvent to obtain a hole transport layer; preparing the OLED device based on the hole transport layer.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 1%-5% of the added volume of the toluene.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 2%-4% of the added volume of the toluene.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 3% of the added volume of toluene.
  • the spin coating speed of the raw material solution is 18000rpm/min-24000rpm/min, and the spin coating time is 10s-2min.
  • another technical solution adopted in the embodiments of the present application is to provide an OLED device, which is prepared according to the above preparation method.
  • another technical solution adopted in the embodiments of the present application is to provide a raw material solution formed by spin coating for application in an OLED device, and the raw material solution includes: (4,4′-cyclohexylene) Bis[N,N-bis(4-methylphenyl)aniline]) and dissolved in (4,4'-cyclohexylenebis[N,N-bis(4-methylphenyl)aniline])
  • the solvent includes methyl benzoate.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 1%-5% of the added volume of the toluene.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 2%-4% of the added volume of the toluene.
  • the solvent is a mixture of toluene and methyl benzoate, and the added volume of the methyl benzoate is 3% of the added volume of toluene.
  • the preparation method of the OLED provided by the examples of the present application, when spin coating (4,4′-cyclohexylene bis[N,N-bis(4-methylphenyl)aniline]) as a hole transport layer, in Methyl benzoate is added to the solvent, which improves the performance of the hole transport layer, improves the mobility of the hole transport layer and the current efficiency of the OLED device. While the preparation process is simple and the cost is low, the OLED device is greatly improved performance.
  • FIG. 1 is a schematic structural diagram of an OLED device provided by an embodiment of the present application.
  • FIG. 3 is a voltage-current density curve diagram of the OLED device provided by the embodiment of the present application.
  • a typical OLED device has an anode, an organic functional layer, and a cathode that are sequentially formed on the substrate.
  • the general organic functional layer may include a single-layer or multi-layer structure.
  • the conventional organic functional layer of the OLED device is described as a multilayer structure.
  • FIG. 1 is a schematic structural diagram of an OLED device 100 provided by an embodiment of the present application. As shown in FIG. 1, the OLED device 100 includes an anode 20 and a hole injection layer sequentially stacked on a substrate 10. 30. Hole transport layer 40, light emitting layer 50, electron transport layer 60, electron injection layer 70, and cathode 80.
  • the preparation process of the OLED device shown in FIG. 1 mainly involves two aspects of surface treatment and preparation of each layer of thin film.
  • the preparation process of each layer of film mainly includes evaporation technology under high vacuum, wet rotation and wet inkjet printing.
  • the preparation process of each layer is selected as follows:
  • the hole injection layer 30 is prepared by wet spin coating
  • the hole transport layer 40 is prepared by evaporation or wet spin coating
  • the light emitting layer 50 is prepared by wet inkjet printing
  • the electron transport layer 60 and electron injection are prepared by vacuum evaporation Layer 70 to obtain the final OLED device 100.
  • TAPC 4,4'-cyclohexylene bis[N,N-bis(4-methylphenyl)aniline]
  • the lowest excited state of TAPC is higher than that of the light-emitting layer
  • the highest excited state of the material will not form a complex with the light-emitting layer material in the excited state, and TAPC has a low affinity for electrons, which can facilitate the injection of holes from the metal cathode.
  • TAPC also has the characteristics of high temperature resistance and good film formation, it can be formed on other functional layers of the OLED device by the above-mentioned vacuum evaporation or wet spin coating process.
  • Vacuum evaporation is to heat TAPC in a vacuum environment and vaporize it to condense to form a solid film; while wet spin coating is to dissolve TAPC in a suitable organic solvent to prepare a solution with a suitable concentration. Then, by adjusting the speed of the homogenizer, the solution is spin-coated on other functional layers, and dried to fix it into a film.
  • the vacuum evaporation deposition is used to prepare the OLED device, and the hole transport layer has good film formation quality and accuracy is easy to control, but the process is complicated and the cost is high.
  • the OLED device prepared by wet spin coating is simple in process, low in cost, and easy to realize, but its film forming quality is not easy to control.
  • the quality of the hole transport layer of the OLED device prepared by the wet spin coating process is not easy to control, it will eventually result in a high operating voltage of the OLED device and a low current efficiency of the device, affecting the performance of the OLED device.
  • the embodiments of the present application improve the conventional hole transport layer of the OLED device prepared by the spin coating method to obtain a hole transport layer with a simple process and good film formation quality.
  • Embodiments of the present application first provide a method for manufacturing an OLED device, and the method includes the following steps:
  • Step 1 Prepare a raw material solution, the solute of the raw material solution is TAPC, and methyl benzoate is added to the solvent.
  • the raw material solution is a raw material solution for dissolving TAPC.
  • the raw material solution includes: TAPC and a solvent for dissolving TAPC, and the solvent is a mixture of toluene and methyl benzoate.
  • the added volume of the methyl benzoate is 1% to 5% of the added volume of the toluene. Adding methyl benzoate to the solvent can help rearrange the TAPC molecules to obtain holes with good film forming quality Transport layer.
  • Step 2 Spin coating the raw material solution and drying the solvent to obtain a hole transport layer.
  • the hole transport layer can be obtained by spin coating the raw material solution on other functional layers using a homogenizer. And by adjusting the concentration of the raw material solution and controlling the speed of the homogenizer to control the thickness of the hole transport layer.
  • Step 3 Prepare the OLED device based on the hole transport layer.
  • the embodiments of the present application further provide an OLED device, which is prepared by the above preparation method.
  • the OLED device prepared by the above method has a high hole transport layer mobility, which improves the performance of the entire OLED device.
  • ITO indium tin oxide
  • PEDOT poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)
  • the TAPC is heated in a vacuum environment and vaporized to condense to form a solid film to obtain a hole transport layer.
  • the OLED devices prepared in the above Examples 1-5 and Comparative Examples 1 and 2 were tested for electrical performance, that is, the current density-current efficiency relationship and the voltage-current density relationship were tested.
  • the test results are shown in FIGS. 2 and 2. 3; the working voltage and current efficiency results of the test are shown in Table 1 below.
  • the current efficiency of the OLED device is between 5.0-6.2 Cd/A, and as the current increases, the trend is to increase first and then decrease.
  • the volume of methyl benzoate is 3%, the current efficiency and current density of the OLED device are close to the performance level of the vacuum evaporation OLED device.
  • the current density of the OLED device reaches the maximum and no longer increases when the operating voltage is between 5-6V.
  • the vacuum evaporation OLED device has the smallest voltage and the current density The largest, the current stability is good, but when the volume of methyl benzoate is 3%, its current density is close to that of vacuum evaporation.
  • the inventor found that when preparing OLED devices by spin coating method in traditional technology, toluene is used as a solvent to dissolve TAPC.
  • toluene is used as a solvent to dissolve TAPC.
  • the TAPC uses toluene as a solvent, due to the low melting point of toluene, its volatilization is rapid, and TAPC If the molecules are too late to rearrange, they will randomly pile up and form an amorphous film, which results in a low hole mobility of the hole transport layer and affects the transmission performance of the entire OLED device.
  • the hole transport layer After adding methyl benzoate to toluene, due to the high boiling point of methyl benzoate, after spin coating, the hole transport layer will remain volatile methyl benzoate, which will promote TAPC After rearrangement, microcrystals are formed in the hole transport layer, so that the mobility of the hole transport layer is increased, so that the performance of the OLED device is improved.
  • the spin coating speed is selected to be 20,000 rpm/min, and the spin coating time is 30 s.
  • the suitable spin coating speed can be 18000rpm/min-24000rpm/min, and the suitable spin coating time can be 10s-2min; moreover, a larger spin coating speed means a shorter spin coating time.
  • the spin coating speed and time can ensure the thickness of the hole transport layer, at the same time, impurities can be thrown away to ensure the cleanness of the hole transport layer film.
  • the OLED can be obtained The performance of the device is the best.
  • the OLED device when TAPC is spin-coated as a hole transport layer, toluene is used as a solvent, and 1-5% methyl benzoate is added to improve the performance of the hole transport layer film and increase the air gap.
  • the mobility of the hole transport layer film and the current efficiency of the device reduce the operating voltage of the device. Compared with vacuum evaporation, its manufacturing process is simple, low cost, easy to realize, and the quality of film formation is reliable.

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

Abstract

L'invention concerne une solution de matière première pour la formation d'un film de revêtement par centrifugation, un dispositif OLED préparé à l'aide de la solution de matière première et son procédé de préparation. Le procédé de préparation consiste à : préparer une solution de matière première, la solution de matière première ayant un soluté de 4,4'-cyclohexylènebis[N,N-bis(4-méthylphényl)aniline] (TAPC), et du benzoate de méthyle est ajouté à un solvant ; revêtir par centrifugation la solution de matière première et sécher le solvant pour obtenir une couche de transport de trous ; et préparer un dispositif OLED sur la base de la couche de transport de trous. Dans un procédé de préparation d'une OLED selon un mode de réalisation, lors du revêtement par centrifugation de TAPC en tant que couche de transport de trous, du benzoate de méthyle est ajouté au solvant, ce qui améliore la mobilité de la couche de transport de trous et l'efficacité actuelle du dispositif OLED, et améliore les performances du dispositif OLED.
PCT/CN2018/119893 2018-12-07 2018-12-07 Dispositif oled et son procédé de préparation, et solution de matière première pour formation de film de revêtement par centrifugation Ceased WO2020113574A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2018/119893 WO2020113574A1 (fr) 2018-12-07 2018-12-07 Dispositif oled et son procédé de préparation, et solution de matière première pour formation de film de revêtement par centrifugation
CN201880095919.XA CN112640151A (zh) 2018-12-07 2018-12-07 Oled器件及其制备方法、旋涂成膜的原料溶液

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PCT/CN2018/119893 WO2020113574A1 (fr) 2018-12-07 2018-12-07 Dispositif oled et son procédé de préparation, et solution de matière première pour formation de film de revêtement par centrifugation

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102124588A (zh) * 2008-07-21 2011-07-13 剑桥显示技术有限公司 用于制造发光器件的组合物和方法
CN104203968A (zh) * 2012-03-23 2014-12-10 E.I.内穆尔杜邦公司 绿色发光材料
CN107108861A (zh) * 2014-11-20 2017-08-29 E.I.内穆尔杜邦公司 空穴传输材料
WO2017216128A1 (fr) * 2016-06-17 2017-12-21 Merck Patent Gmbh Formulation de matiere fonctionnelle organique
WO2018017288A1 (fr) * 2016-07-20 2018-01-25 E. I. Du Pont De Nemours And Company Matériaux électroactifs
CN107925001A (zh) * 2015-08-11 2018-04-17 E.I.内穆尔杜邦公司 空穴传输材料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1850368B2 (fr) * 2005-02-15 2021-04-21 Pioneer Corporation Composition filmogène et dispositif électroluminescent organique
CN111477766B (zh) * 2015-06-12 2023-04-07 默克专利有限公司 作为用于oled制剂的溶剂的含有非芳族环的酯
CN106633005B (zh) * 2017-01-04 2019-10-18 华南理工大学 含寡聚醚侧链的三苯胺类聚合物及其在溶液法制备有机光电器件中的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102124588A (zh) * 2008-07-21 2011-07-13 剑桥显示技术有限公司 用于制造发光器件的组合物和方法
CN104203968A (zh) * 2012-03-23 2014-12-10 E.I.内穆尔杜邦公司 绿色发光材料
CN107108861A (zh) * 2014-11-20 2017-08-29 E.I.内穆尔杜邦公司 空穴传输材料
CN107925001A (zh) * 2015-08-11 2018-04-17 E.I.内穆尔杜邦公司 空穴传输材料
WO2017216128A1 (fr) * 2016-06-17 2017-12-21 Merck Patent Gmbh Formulation de matiere fonctionnelle organique
WO2018017288A1 (fr) * 2016-07-20 2018-01-25 E. I. Du Pont De Nemours And Company Matériaux électroactifs

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