WO2020113574A1 - Oled器件及其制备方法、旋涂成膜的原料溶液 - Google Patents

Oled器件及其制备方法、旋涂成膜的原料溶液 Download PDF

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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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Prior art keywords
oled device
methyl benzoate
raw material
toluene
transport layer
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French (fr)
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闵超
李灵芝
王超
赖瑞云
舒鹏
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Shenzhen Royole Technologies Co Ltd
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Shenzhen Royole Technologies Co Ltd
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Priority to PCT/CN2018/119893 priority Critical patent/WO2020113574A1/zh
Priority to CN201880095919.XA priority patent/CN112640151A/zh
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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

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  • 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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Abstract

一种旋涂成膜的原料溶液，使用该原料溶液制备的OLED器件及其制备方法。该制备方法包括：制备原料溶液，该原料溶液的溶质为4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺](TAPC)，溶剂中添加有苯甲酸甲酯；旋涂原料溶液，并烘干溶剂，得到空穴传输层；基于空穴传输层制备OLED器件。实施例提供的OLED的制备方法在旋涂TAPC作为空穴传输层时，在溶剂中添加了苯甲酸甲酯，提高了空穴传输层的迁移率和OLED器件的电流效率，改善了OLED器件的性能。

Description

OLED器件及其制备方法、旋涂成膜的原料溶液 技术领域
本申请涉及显示技术领域，特别是涉及一种OLED器件及其制备方法、一种旋涂成膜的原料溶液。
背景技术
有机电致发光器件(Organic Light-Emitting Diode,OLED)为自发光器件，以其形体薄、面积大、柔性化等优点引起人们的广泛关注，在显示与照明领域有着重要应用。
典型的OLED器件具有依次形成于基板上的阳极、有机功能层和阴极。其中，依据不同的设计或者需要，该OLED器件的有机功能层可以具有不同的结构，例如，有机功能层包括用于空穴的注入和传输的空穴传输层。空穴传输层的制备工艺在很大程度上影响OLED器件的性能和长期稳定性。
发明人在实现本发明的过程中发现，利用传统材料和旋涂法制备空穴传输层，虽然工艺简单，制作成本低，但是其最终制得的OLED器件电流效率低，OLED器件性能不佳。
发明内容
本申请旨在提供一种OLED器件的制备方法及OLED器件、一种旋涂成膜的原料溶液，以解决传统制备工艺得到的OLED器件，电流效率低、器件性能不佳的技术问题。
为解决上述技术问题，本申请实施例采用的一个技术方案是：提供一种OLED器件的制备方法，包括：制备原料溶液，所述原料料溶液的溶质为TAPC，溶剂中添加有苯甲酸甲酯；旋涂所述原料溶液，并烘干所述溶剂，得到空穴传输层；基于所述空穴传输层制备所述OLED器件。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的1％-5％。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的2％-4％。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的3％。
可选地，旋涂所述原料溶液的旋涂速度为18000rpm/min--24000rpm/min，旋涂时间为10s-2min。
为解决上述技术问题，本申请实施例采用的另一个技术方案是：提供一种OLED器件，所述OLED器件按照上述制备方法制备得到。
为解决上述技术问题，本申请实施例采用的另一个技术方案是：提供一种旋涂成膜的原料溶液，应用于OLED器件中，所述原料溶液包括：(4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])和溶解所述(4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])中的溶剂，所述溶剂包括苯甲酸甲酯。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的1％-5％。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的2％-4％。
可选地，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的3％。
本申请实施例提供的OLED的制备方法，其在旋涂(4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])作为空穴传输层时，在溶剂中添加了苯甲酸甲酯，改善了空穴传输层的性能，提高了空穴传输层的迁移率和OLED器件的电流效率，在制备工艺简单、成本低的同时，大大改善了OLED器件的性能。
附图说明
图1是本申请实施例提供的一种OLED器件的结构示意图；
图2是本申请实施例提供的OLED器件的电流密度—电流效率曲线图；
图3是本申请实施例提供的OLED器件的电压—电流密度曲线图。
具体实施方式
为了使本申请的目的、方案及优点更加清楚明白，以下结合实施例，对本 申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。此外，下面所描述的本申请不同实施例中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
典型的OLED器件具有依次形成于基板上的阳极、有机功能层和阴极。一般有机功能层可以包括单层或多层结构。本申请实施例即以惯常的OLED器件的有机功能层为多层结构进行说明。具体请参阅图1，图1是本申请实施例提供的一种OLED器件100的结构示意图，如图1所示，所述OLED器件100包括依次层叠于基板10上的阳极20、空穴注入层30、空穴传输层40、发光层50、电子传输层60、电子注入层70和阴极80。
图1所示的OLED器件的制备工艺主要涉及表面处理和各层薄膜制备两方面。其中，各层薄膜制备工艺主要包括高真空下的蒸镀技术、湿法旋转以及湿法喷墨打印。其各层的制备工艺选择如下：
通过湿法旋涂制备空穴注入层30，通过蒸镀或者湿法旋涂制备空穴传输层40，通过湿法喷墨打印制备发光层50，通过真空蒸镀制备电子传输层60和电子注入层70以得到最终的OLED器件100。
其中，传统的空穴传输层的材料选用：TAPC(4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])，TAPC的最低激发态高于发光层材料的最高激发态，不会在激发态下与发光层材料形成复合物，并且TAPC对电子的亲和能力低，可以方便空穴从金属阴极注入。由于TAPC还具有耐高温和成膜性好的特点，因此其可以通过上述真空蒸镀或者湿法旋涂工艺成膜于OLED器件的其他功能层上。
真空蒸镀即为将TAPC置于真空环境中加热，并使之气化以凝结形成固态薄膜；而湿法旋涂即是将TAPC溶于适当的有机溶剂中，配成合适浓度的溶液。然后通过调节匀胶机的转速，以将溶液旋涂在其他功能层上，并烘干，使其固定成膜。其中，利用真空蒸镀制备OLED器件，其空穴传输层成膜质量好，精度易于控制，但是工艺复杂，成本高。而湿法旋涂制备的OLED器件则工艺简单，成本低，易于实现，但是其成膜质量则不容易控制。
由于湿法旋涂工艺制备的OLED器件，其空穴传输层的质量不容易控制，最终会导致OLED器件的工作电压高，器件电流效率低，影响OLED器件性能。
基于此，本申请实施例对传统的利用旋涂法制备OLED器件的空穴传输层进行改进，以得到工艺简单且成膜质量好的空穴传输层。
本申请实施例首先提供一种制备OLED器件的制备方法，所述方法包括如下步骤：
步骤1、制备原料溶液，所述原料溶液的溶质为TAPC，溶剂中添加有苯甲酸甲酯。
所述原料溶液为溶解TAPC的原料溶液，在本实施例中所述原料溶液包括：TAPC和溶解TAPC的溶剂，所述溶剂为甲苯与苯甲酸甲酯的混合物。
较佳地，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的1％-5％，在溶剂中添加苯甲酸甲酯，可以帮助TAPC分子重新排列，得到成膜质量好的空穴传输层。
步骤2、旋涂所述原料溶液，并烘干所述溶剂，得到空穴传输层。
此步骤可以使用匀胶机将原料溶液旋涂在其他功能层上来得到空穴传输层。并通过调节原料溶液的浓度和控制匀胶机的转速来控制空穴传输层的厚度。
步骤3、基于所述空穴传输层制备所述OLED器件。
所述OLED器件其他各层的制备方法均可以基于传统技术实现，在此不再赘述。
本申请实施例还提供一种OLED器件，该OLED器件由上述制备方法制备得到。上述方法制备得到的OLED器件，其空穴传输层迁移率高，使整个OLED器件性能得到提升。
本申请实施例提供的OLED的制备方法，其在旋涂TAPC作为空穴传输层时，以甲苯作为溶剂，并添加了苯甲酸甲酯，改善了空穴传输层的性能，提高了空穴传输层的迁移率和OLED器件的电流效率，在制备工艺简单的同时，大大改善了OLED器件的性能。
以下结合具体实施例，详细描述OLED器件的制备方法。
实施例1
1.在洁净的导电基板上光刻涂覆ITO(氧化铟锡)阳极；
2.在该阳极上旋涂PEDOT：PSS(聚(3,4-亚乙基二氧噻吩)/聚(4-苯乙烯磺酸盐))形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯与苯甲酸甲酯，苯甲酸甲酯的添加体积是甲苯添加体积的1％；
4.通过喷墨工艺在空穴传输层上涂布CBP(4,4'-双(N-咔唑基)-1,1'-联苯)形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi(1,3,5-三(1-苯基-1H-苯并[d]咪唑-2-基)苯基)、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
实施例2
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯与苯甲酸甲酯，苯甲酸甲酯的添加体积是甲苯添加体积的2％；
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
实施例3
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯与苯甲酸甲酯，苯甲酸甲酯的添加体 积是甲苯添加体积的3％；
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
实施例4
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯与苯甲酸甲酯，苯甲酸甲酯的添加体积是甲苯添加体积的4％；
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
实施例5
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯与苯甲酸甲酯，苯甲酸甲酯的添加体积是甲苯添加体积的5％；
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
对比例1
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.在空穴注入层上旋涂TAPC溶液，旋涂速度为2000rpm/min，旋涂持续时间为1min，然后放到120℃烘箱中30min烘干，得到空穴传输层，空穴传输层厚度为30nm；TAPC溶液中的溶剂为：甲苯；
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
对比例2
1.在洁净的导电基板上光刻涂覆ITO阳极；
2.在该阳极上旋涂PEDOT：PSS形成空穴注入层，空穴注入层厚度为60nm；
3.将TAPC置于真空环境中加热，并使之气化以凝结形成固态薄膜得到空穴传输层。
4.通过喷墨工艺在空穴传输层上涂布CBP形成发光层，该发光层的厚度为30nm；
5.通过蒸镀工艺依次在发光层上蒸镀TPBi、氟化锂和铝，形成厚度为35nm的电子传输层、厚度为1nm的电子注入层和厚度为100nm的阴极。
6.采用封装盖板对各层进行整体封装，制备得到OLED器件。
将上述实施例1-5和对比例1和2制备得到的OLED器件，进行电学性能测试，即测试其电流密度—电流效率的关系以及电压—电流密度的关系，其测试结果如图2和图3所示；其测试的工作电压和电流效率结果如下表1所示。
表1
Figure PCTCN2018119893-appb-000001
Figure PCTCN2018119893-appb-000002
由图2可知，OLED器件的电流效率在5.0-6.2Cd/A之间，并且随着电流的增大呈现先增大后减小的趋势。在苯甲酸甲酯的体积为3％时，OLED器件的电流效率和电流密度接近真空蒸镀OLED器件的性能水平。
由图3可知，在工作电压在5-6V之间，OLED器件的电流密度达到最大并且不再增加，相对于湿法旋涂制备空穴传输层，真空蒸镀OLED器件其电压最小，电流密度最大，电流稳定性好，但在苯甲酸甲酯的体积为3％时，其电流密度接近真空蒸镀的电流密度。
发明人在实现本发明的过程中发现：传统技术通过旋涂法制备OLED器件时，其采用甲苯做为溶剂来溶解TAPC，该TAPC用甲苯做溶剂时，由于甲苯熔点低，其挥发迅速，TAPC分子来不及重新排列会出现随机堆积，形成无定型薄膜，这样导致空穴传输层的空穴迁移率低，影响整个OLED器件的传输性能。
而在甲苯中添加苯甲酸甲酯后，由于苯甲酸甲酯的沸点高，在旋涂成膜后，空穴传输层中会残留挥发后的苯甲酸甲酯，该苯甲酸甲酯会促进TAPC重新排列，在空穴传输层形成微晶，这样空穴传输层的迁移率增大，使得OLED器件的性能提升。
由上述测试结果可知，在用旋涂法制备空穴传输层时，相对于传统的以单一甲苯做溶剂，在甲苯溶剂中添加体积是1％-5％的苯甲酸甲酯时,其工作电压有下降趋势，电流效率有增大趋势，并且在苯甲酸甲酯的体积为3％时，工作电压最小，电流效率最高，OLED器件的性能最好，已经接近真空蒸镀OLED器件的性能水平。
本申请实施例1-5和对比例1在旋涂制备空穴传输层时，选用的旋涂速度为20000rpm/min，旋涂时间为30s。但其合适的旋涂速度可以为18000rpm/min--24000rpm/min，合适的旋涂时间可以为10s-2min；并且，较大的旋涂速度意味着较短的旋涂时间。该旋涂速度和时间可以保证空穴传输层厚度的 同时，还可以将杂质甩去，以保证空穴传输层薄膜的清洁，在该限定旋涂速度和旋涂时间范围内，能得到的OLED器件的性能最佳。
本申请实施实例提供的OLED器件，其在旋涂TAPC作为空穴传输层时，以甲苯作为溶剂，并添加1-5％苯甲酸甲酯，改善了空穴传输层薄膜的性能，提高了空穴传输层薄膜的迁移率和器件的电流效率，降低了器件的工作电压。相对于真空蒸镀，其制作工艺简单，成本低，易于实现，并且成膜质量可靠。
以上所述仅为本申请的实施例，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (10)

  1. 一种OLED器件的制备方法，其特征在于，包括：
    制备原料溶液，所述原料溶液的溶质为TAPC，溶剂中添加有苯甲酸甲酯；
    旋涂所述原料溶液，并烘干所述溶剂，得到空穴传输层；
    基于所述空穴传输层制备所述OLED器件。
  2. 根据权利要求1所述的制备方法，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的1％-5％。
  3. 根据权利要求2所述的制备方法，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的2％-4％。
  4. 根据权利要求3所述的制备方法，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的3％。
  5. 根据权利要求1所述的制备方法，其特征在于，旋涂所述原料溶液的旋涂速度为18000rpm/min--24000rpm/min，旋涂时间为10s-2min。
  6. 一种OLED器件，其特征在于，所述OLED器件按照权利要求1-5任一项所述的制备方法制备得到。
  7. 一种旋涂成膜的原料溶液，应用于OLED器件中，其特征在于，所述原料溶液包括：
    (4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])和溶解所述(4,4'-亚环己基双[N,N-双(4-甲基苯基)苯胺])中的溶剂，所述溶剂包括苯甲酸甲酯。
  8. 根据权利要求7所述的原料溶液，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的1％-5％。
  9. 根据权利要求8所述的原料溶液，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的2％-4％。
  10. 根据权利要求9所述的原料溶液，其特征在于，所述溶剂为甲苯与苯甲酸甲酯的混合物，所述苯甲酸甲酯的添加体积为所述甲苯添加体积的3％。
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