WO2022088111A1 - 基于热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法 - Google Patents

基于热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法 Download PDF

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WO2022088111A1
WO2022088111A1 PCT/CN2020/125583 CN2020125583W WO2022088111A1 WO 2022088111 A1 WO2022088111 A1 WO 2022088111A1 CN 2020125583 W CN2020125583 W CN 2020125583W WO 2022088111 A1 WO2022088111 A1 WO 2022088111A1
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fluorescent material
thermally activated
activated delayed
delayed fluorescent
electroluminescent device
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PCT/CN2020/125583
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English (en)
French (fr)
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李艳青
谢凤鸣
唐建新
周经雄
曾馨逸
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苏州大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass

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  • the invention relates to the field of organic electroluminescent materials, in particular to an ultra-thick non-doped electroluminescent device based on thermally activated delayed fluorescent materials, which can be industrialized, has a simple preparation method and good performance, and a preparation method thereof.
  • Electroluminescence (English electroluminescent), also known as electric field luminescence, or EL for short, is to generate an electric field through the voltage applied to the two electrodes, and the electrons excited by the electric field hit the luminescent center, causing electrons to transition, change, and A physical phenomenon in which recombination leads to luminescence. It is generally believed that under the action of a strong electric field, the energy of the electrons increases accordingly until it far exceeds the energy of the electrons in the thermal equilibrium state and becomes superheated electrons. During the movement process, the superheated electrons can ionize the lattice through collision to form electrons and empty electrons.
  • Electroluminescence can be divided into high-field electroluminescence and low-field electroluminescence from the light-emitting principle. High-field electroluminescence is an in vivo luminescence effect.
  • a light-emitting material is a semiconductor compound, in which holes and electrons recombine in the light-emitting layer to form excitons, but most light-emitting materials suffer from the phenomenon of aggregation concentration quenching (ACQ), which requires low concentration doping in the host material as the light-emitting layer. It is difficult to precisely control the doping ratio, the co-evaporation preparation process is complicated, and the luminous efficiency is very poor in the case of high concentration doping, or even without doping the host material. At the same time, when the thickness of the light emitting layer is very thick, the turn-on voltage will also be very large. .
  • the non-doped light-emitting material can greatly simplify the process of preparing electroluminescent devices, and the ultra-thick light-emitting layer can solve the problem of large-area preparation of OLEDs in industry.
  • TADF organic light-emitting materials can theoretically achieve 100% internal quantum efficiency without noble metals, which has become a research hotspot.
  • TADF materials that have both non-doped properties and can emit light efficiently in ultra-thick thin films are rare, so it is simple to develop new ones.
  • High-efficiency non-doped TADF materials have become a current research hotspot.
  • the invention discloses an ultra-thick undoped electroluminescence device of a chiral thermally activated delayed fluorescent material and a preparation method thereof.
  • the chemical name of the chiral thermally activated delayed fluorescent material is 3,5-bis(9H-carbazole- 9-yl)-2,4,6-tris(3,6-di-tert-butyl-9H-carbazol-9-yl) benzonitrile, to solve the problem of difficult synthesis and preparation of delayed fluorescence luminescent materials, few types of materials and raw materials At the same time, it solves the problems of complex preparation process of electroluminescent devices and difficult preparation of large-area devices; especially, the OLED prepared by the ultra-thick undoped light-emitting layer of the thermally activated delayed fluorescent material realizes its EQE over 20%, low efficiency roll-off target.
  • the present invention adopts the following technical solutions.
  • An ultra-thick undoped electroluminescent device based on thermally activated delayed fluorescent material comprising a thermally activated delayed fluorescent material undoped ultra-thick light-emitting layer; the light-emitting layer of the ultra-thick undoped electroluminescent device according to the present invention It is composed of its own thermally activated delayed fluorescent material; further, the thickness of the light-emitting layer of the thermally activated delayed fluorescent material is 50-200 nm.
  • the ultrathick undoped electroluminescent device based on thermally activated delayed fluorescent material disclosed in the present invention is composed of an anode, a hole injection layer, a hole transport layer, a blocking layer, an ultrathick undoped light-emitting layer, an electron transport layer, an electron injection layer Layer, cathode composition; specifically, indium tin oxide (ITO) is used as anode, bispyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7, 10,11-Capronitrile (HATCN) was used as a hole injection layer (HIL), 4,4'-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline) ( TAPC) as hole transport layer (HTL), 1,3-bis(9H-carbazol-9-yl)benzene (mCP) as electron/exciton blocking layer (EBL), the thermally activated delayed fluorescent material Used as light-e
  • the invention discloses an ultra-thick undoped light-emitting layer for an electroluminescent device, which is a thermally activated delayed fluorescent material 3,5-bis(9H-carbazol-9-yl)-2,4,6-tris(3 , 6-di-tert-butyl-9H-carbazol-9-yl) benzonitrile alone.
  • the preparation method of the above-mentioned ultra-thick undoped electroluminescent device based on thermally activated delayed fluorescent material is as follows: vacuum evaporation of a hole injection layer, a hole transport layer, a blocking layer, an ultra-thick undoped light-emitting layer, An electron transport layer, an electron injection layer, and a cathode are used to obtain the ultrathick undoped electroluminescence device based on the thermally activated delayed fluorescent material. Vacuum evaporation is a conventional technique.
  • the thermally activated delayed fluorescent material of the present invention has the following chemical structural formula.
  • the preparation method of the above thermally activated delayed fluorescent material comprises the following steps: using 2,3,4,5,6-pentafluorobenzonitrile, 3,6-di-tert-butyl-9H-carbazole and 9H-carbazole as raw materials,
  • the green thermally activated delayed fluorescent material is prepared by a continuous one-pot reaction; the reaction can be referred to as follows.
  • reaction solution is poured into water, and then a large amount of solid is obtained by suction filtration.
  • product is separated and purified by column chromatography (petroleum ether/dichloromethane, volume ratio is 4:1) to obtain the thermal activation delay. fluorescent material.
  • the invention provides a method for synthesizing and preparing a novel thermally activated delayed fluorescent material; and an ultra-thick undoped electroluminescent device based on the thermally activated delayed fluorescent material, which achieves the goal of having an EQE exceeding 20% and a low-efficiency roll-off; It is used to solve the problems of difficult synthesis and preparation of delayed fluorescent light-emitting materials, few types of materials, expensive raw materials, and quenching of aggregation concentration; meanwhile, it solves the problems of complex preparation process of electroluminescent devices and difficult preparation of large-area devices.
  • the organic thin film formed by the invention has high surface smoothness, stable chemical and physical properties and high luminous efficiency, and the formed ultra-thick undoped organic electroluminescent device has good performance.
  • Thermally activated delayed fluorescence materials have the characteristics of twisted internal charge transfer (TICT), and at the same time have typical thermally activated delayed fluorescence (TADF) properties, 100% high fluorescence quantum yield (PLQY) and high thermal stability and other advantages, more importantly What is interesting is that this compound has no aggregation concentration quenching (ACQ) effect in the pure film state.
  • the ultrathick undoped organic electroluminescence device based on the thermally activated delayed fluorescent material provided by the present invention has the advantages of low driving voltage and good luminescence stability, and the external quantum efficiency EQE of the prepared device is as high as 21.1%, which is Efficiency rolls off at high brightness.
  • the thermally activated delayed fluorescent material provided by the present invention has few synthesis and preparation steps, readily available raw materials, simple synthesis and purification processes, high yield, and can be synthesized and prepared on a large scale.
  • Organic electroluminescent devices based on it have good application prospects in the fields of large-area lighting and flat panel displays.
  • Figure 1 is the hydrogen NMR spectrum of Compound A prepared in Example 1.
  • FIG. 2 is the carbon nuclear magnetic spectrum of compound A prepared in Example 1.
  • FIG. 3 is the mass spectrum of Compound A prepared in Example 1.
  • FIG. 4 is an efficiency diagram of the devices of Examples 1 to 4.
  • FIG. 4 is an efficiency diagram of the devices of Examples 1 to 4.
  • FIG. 5 is an efficiency diagram of a device of Comparative Example 1.
  • FIG. 6 is a graph of the efficiency of the device of Comparative Example 2.
  • the raw materials involved in the present invention are all conventional commercial products, and the specific operation methods and testing methods are conventional methods in the field; especially the specific preparation process and the materials of each layer of the organic electroluminescent device based on the thermally activated delayed fluorescent material of the present invention are existing Techniques, such as vacuum evaporation, the vacuum degree is ⁇ 2 ⁇ 10 -4 Pa, the deposition rate of functional layer is 2 ⁇ /s, the deposition rate of host material is 1 ⁇ /s, the deposition rate of LiF layer is 0.1 ⁇ /s, the deposition rate of Al The deposition rate was 8 ⁇ /s.
  • the inventiveness of the present invention is to provide a new thermally activated delayed fluorescent material with non-doped properties, and the ultra-thick non-doped material can be used alone as a light-emitting layer of an organic electroluminescence device.
  • the present invention provides an efficient green thermally activated delayed fluorescent material 3,5-bis(9H-carbazol-9-yl)-2,4,6-tris(3,6-di-tert-butyl-9H-carbazole- 9-yl) benzonitrile (compound A).
  • the reaction formula is as follows.
  • the reaction is specifically as follows.
  • Fig. 1 is the hydrogen nuclear magnetic spectrum of the compound A obtained above
  • Fig. 2 is the carbon nuclear magnetic spectrum of the compound A obtained above
  • Fig. 3 is the mass spectrum of the compound A obtained above.
  • the structure detection of compound A is as follows.
  • Example 1 Fabrication and performance evaluation of an organic electroluminescent device with 50 nm material A as the light-emitting layer.
  • the fabrication steps of the organic electroluminescent device with 50 nm material A as the light-emitting layer are as follows.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/A (50 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); the specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Example 2 Fabrication and performance evaluation of an organic electroluminescent device with 100 nm material A as the light-emitting layer.
  • the fabrication steps of the organic electroluminescent device with 100 nm material A as the light-emitting layer are as follows.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows. ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/A (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); Plating is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Example 3 Fabrication and performance evaluation of an organic electroluminescent device with 150 nm material A as the light-emitting layer.
  • the fabrication steps of the organic electroluminescent device with 150 nm material A as the light-emitting layer are as follows.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/A (150 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); the specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Example 4 Fabrication and performance evaluation of an organic electroluminescent device with 200 nm material A as the light-emitting layer.
  • the fabrication steps of the organic electroluminescent device with 200 nm material A as the light-emitting layer are as follows.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/A (200 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); the specific layer evaporation is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows. ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/ B (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); Plating is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Direct current was applied to the fabricated organic electroluminescent device, and the luminescence performance was evaluated by using an integrating sphere; the current-voltage characteristics were measured by a computer-controlled Keithley 2400 digital source meter.
  • the luminescence properties of the organic electroluminescent device were measured under the condition of changing the applied DC voltage.
  • the device performance is shown in Figure 5.
  • the turn-on voltage is 3.5 V
  • the maximum external quantum efficiency is 8.4%
  • the electroluminescence peak is 525 nm.
  • Pretreatment of glass anode select a glass substrate (3 ⁇ 3 mm) with an indium tin oxide (ITO) film pattern as a transparent electrode; after cleaning the glass substrate with ethanol, UV-ozone processing to obtain a pretreated glass substrate.
  • ITO indium tin oxide
  • Vacuum evaporation vacuum evaporation of each layer is carried out on the pretreated glass substrate by vacuum evaporation method, and the treated glass substrate is placed in a vacuum evaporation chamber, and the degree of vacuum is ⁇ 2 ⁇ 10 ⁇ 4 Pa, the device structure is as follows. ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/C (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm); Plating is a conventional technique.
  • Device packaging seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water oxygen concentration of less than 1 ppm, and then cover the above-mentioned film formation with a sealing cover with epoxy UV-curable resin glass.
  • the substrate is sealed by UV curing; the specific encapsulation is conventional technology.
  • Direct current was applied to the fabricated organic electroluminescent device, and the luminescence performance was evaluated by using an integrating sphere; the current-voltage characteristics were measured by a computer-controlled Keithley 2400 digital source meter.
  • the luminescence properties of the organic electroluminescent device were measured under the condition of changing the applied DC voltage.
  • the device performance is shown in Figure 6, the turn-on voltage is 7.0 V, the maximum external quantum efficiency is 14.8%, and the electroluminescence peak is 514 nm.

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Abstract

提供一种基于热激活延迟荧光材料的超厚非掺杂电致发光器件，包括热激活延迟荧光材料的超厚非掺杂发光层，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、超厚非掺杂发光层、电子传输层、电子注入层、阴极，得到所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件。所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件可发射绿色荧光(λ＝520nm)，器件外量子效率(EQE)高达21.1％，效率滚降小，且具有驱动电压低，发光稳定性好等优点。

Description

基于热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法 技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种可工业化、制备方法简单、性能好的基于热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法。
 背景技术
电致发光(英文electroluminescent)，又可称电场发光，简称EL，是通过加在两电极的电压产生电场，被电场激发的电子碰击发光中心，而引致电子在能级间的跃迁、变化、复合导致发光的一种物理现象。一般认为是在强电场作用下，电子的能量相应增大，直至远远超过热平衡状态下的电子能量而成为过热电子，这过热电子在运动过程中可以通过碰撞使晶格离化形成电子、空穴对，当这些被离化的电子、空穴对复合或被激发的发光中心回到基态时便发出光来。从发光原理电致发光可以分为高场电致发光和低场电致发光。高场电致发光是一种体内发光效应。
发光材料是一种半导体化合物，空穴和电子在发光层复合形成激子发光，但是大部分发光材料都会遭受聚集浓度淬灭（ACQ）现象，需要低浓度掺杂在主体材料中作为发光层，掺杂比例难以精确控制，共蒸制备工艺复杂，而且在高浓度掺杂，甚至不掺杂主体材料的情况下发光效率很差，同时，在发光层厚度很厚时，开启电压也会很大。因此，具有非掺杂性质的发光材料可以极大的简化制备电致发光器件的工艺，且超厚发光层能够解决工业上大面积制备OLED的难题。TADF有机发光材料无需贵金属即可理论上实现100 %的内量子效率而成为研究的热点，兼具非掺杂性质和可在超厚薄膜状态下高效发光的TADF材料实属罕见，因此开发新型简单、高效的非掺杂TADF材料成为当前的一个研究热点。
 技术问题
本发明公开了一种手性热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法，手性热激活延迟荧光材料的化学名称为3,5-二（9H-咔唑-9-基）-2,4,6-三（3,6-二叔丁基-9H-咔唑-9 -基）苯腈，用以解决延迟荧光发光材料合成制备难、材料种类少、原料昂贵、聚集浓度淬灭的难题；同时解决电致发光器件制备工艺复杂，大面积器件制备难的问题；尤其是，该热激活延迟荧光材料的超厚非掺杂发光层制备的OLED，实现其EQE超过20%，低效率滚降的目标。
 技术解决方案
本发明采用如下技术方案。
一种基于热激活延迟荧光材料的超厚非掺杂电致发光器件，包括热激活延迟荧光材料非掺杂的超厚发光层；本发明所述超厚非掺杂电致发光器件的发光层为所属热激活延迟荧光材料单独组成；进一步的，所述热激活延迟荧光材料发光层的厚度为50~200 nm。
本发明公开的基于热激活延迟荧光材料的超厚非掺杂电致发光器件由阳极、空穴注入层、空穴传输层、阻挡层、超厚非掺杂发光层、电子传输层、电子注入层、阴极组成；具体可以为，氧化铟锡（ITO）用作阳极、双吡嗪并[2,3-f：2'，3'-h]喹喔啉-2,3,6,7,10,11-己腈（HATCN）用作空穴注入层（HIL）、4,4'-（环己烷-1,1-二基）双（N，N-二-对甲苯基苯胺）（TAPC）用作空穴传输层（HTL）、1,3-双（9H-咔唑-9-基）苯(mCP)用作电子/激子阻挡层（EBL）、所述热激活延迟荧光材料用作发光层（EML）、4,6-双（3,5-二（吡啶-3-基）苯基）-2-甲基嘧啶(TMPYPB)用作电子传输层（ETL）、氟化锂（LiF）用作电子注入层（EIL）、铝（Al）用作阴极；进一步的，有机电致发光器件各层规格为：ITO/HATCN（10 nm）/TAPC（60 nm）/mCP（10 nm）/ TADF材料（50-200 nm）/TMPYPB（45 nm）/LiF（1 nm）/Al（100 nm）。
本发明公开了一种电致发光器件用超厚非掺杂发光层，为热激活延迟荧光材料3,5-二（9H-咔唑-9-基）-2,4,6-三（3,6-二叔丁基-9H-咔唑-9 -基）苯腈单独组成。
上述基于热激活延迟荧光材料的超厚非掺杂电致发光器件的制备方法为，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、超厚非掺杂发光层、电子传输层、电子注入层、阴极，得到所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件。真空蒸镀为常规技术。
本发明所述热激活延迟荧光材料，其化学结构式如下。
Figure 87638dest_path_image001
。
上述热激活延迟荧光材料的制备方法包括以下步骤：以2,3,4,5,6-五氟苯腈、3,6-二叔丁基-9H-咔唑和9H-咔唑为原料，连续一锅法反应制备得到所述绿色热激活延迟荧光材料；反应可参考如下。
Figure 70638dest_path_image002
。
反应完毕后，反应液倒入水中，然后再抽滤得大量固体，产物采用柱层析（石油醚/二氯甲烷，体积比为4：1）的方法进行分离提纯，得到所述热激活延迟荧光材料。
本发明提供一种新型热激活延迟荧光材料的合成制备方法；以及基于所述热激活延迟荧光材料的超厚非掺杂电致发光器件，实现其EQE超过20%，低效率滚降的目标；用以解决延迟荧光发光材料合成制备难、材料种类少、原料昂贵、聚集浓度淬灭的难题；同时解决电致发光器件制备工艺复杂，大面积器件制备难的问题。
对于本发明所述的基于热激活延迟荧光材料所形成的超厚非掺杂有机电致发光器件的制备方法以及其他原料没有特殊的限制。利用本发明所形成的有机薄膜具有高表面光滑性、化学物理性质稳定高发光效率，所形成的超厚非掺杂有机电致发光器件性能良好。
 有益效果
本发明有益效果如下。
1.本发明提供的3,5-二（9H-咔唑-9-基）-2,4,6-三（3,6-二叔丁基-9H-咔唑-9 -基）苯腈热激活延迟荧光材料具有扭曲的内电荷转移（TICT）的特点，同时具有典型的热激活延迟荧光（TADF）性质，100%的高荧光量子产率（PLQY）和高热稳定性等优点，更重要的是此化合物在纯膜状态下没有聚集浓度淬灭（ACQ）效应。
2. 基于本发明提供的热激活延迟荧光材料的超厚非掺杂有机电致发光器件，具有驱动电压低，发光稳定性好的优点，且制备的器件的外量子效率EQE高达21.1%，在高亮度下效率滚降低。
3. 本发明提供的热激活延迟荧光材料合成制备步骤少，原料易得，合成及纯化工艺简单，产率高，可大规模合成制备。基于其的有机电致发光器件在大面积照明和平板显示等领域具有很好的应用前景。
 附图说明
图1是实施例1制备所得的化合物A的核磁氢谱。
图2是实施例1制备所得的化合物A的核磁碳谱。
图3是实施例1制备所得的化合物A的质谱。
图4是实施例一到四器件的效率图。
图5是对比例一器件的效率图。
图6是对比例二器件的效率图。
 本发明的实施方式
本发明涉及的原料都为常规市售产品，具体操作方法以及测试方法为本领域常规方法；尤其基于本发明热激活延迟荧光材料的有机电致发光器件的具体制备过程以及各层材料为现有技术，比如真空蒸镀，真空度≤2×10 -4 Pa，功能层沉积速率为2 Å/s，主体材料的沉积速率为1 Å/s，LiF层沉积速率为0.1 Å/s，Al的沉积速率8 Å/s。本发明的创造性在于提供新的具有非掺杂性质的热激活延迟荧光材料，且超厚非掺杂单独作为有机电致发光器件的发光层。
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明提供一种高效绿色热激活延迟荧光材料3,5-二（9H-咔唑-9-基）-2,4,6-三（3,6-二叔丁基-9H-咔唑-9 -基）苯腈（化合物A）。
结构式如下所示。
Figure 934689dest_path_image003
。
合成例。
反应式如下。
Figure 749061dest_path_image004
。
反应具体如下。
150 mL三口烧瓶中加入3.50 g(12.52 mmol) 3,6-二叔丁基-9H-咔唑和15 mL N,N`-二甲基甲酰胺（DMF），在冰浴条件下加入0.26 g(10.83 mmol)NaH，然后在氮气的保护下搅拌30分钟，得到混合溶液。150 mL三口烧瓶中加入1.50 g(8.97 mmol)9H-咔唑和10 mL DMF，在冰浴条件下加入0.22 g(9.12 mmol)NaH，然后在氮气的保护下搅拌30分钟，得到混合液；将混合溶液加入到30 mL含0.80 g(4.14 mmol) 2,3,4,5,6-五氟苯腈的DMF中，室温下反应12小时，然后加入混合液，氮气保护下120 ℃加热反应12小时；然后将反应液倒入水中，析出大量固体，抽滤，产物采用柱层析（石油醚/二氯甲烷，体积比为4：1）的方法进行分离提纯，得到绿色固体3,5-二（9H-咔唑-9-基）-2,4,6-三（3,6-二叔丁基-9H-咔唑-9 -基）苯腈，为化合物A，产率为53%。
图1是上述所得的化合物A的核磁氢谱；图2是上述所得的化合物A的核磁碳谱；图3是上述所得的化合物A的质谱。化合物A结构检测具体如下。
1H NMR (400 MHz, CDCl 3) δ 7.66 (d, J = 1.5 Hz, 4H), 7.26 (d, J = 7.4 Hz, 4H), 7.23 (d, J = 1.8 Hz, 2H), 7.10 (d, J = 8.6 Hz, 4H), 7.04 (dd, J = 8.6, 1.8 Hz, 6H), 6.93 (d, J = 8.2 Hz, 4H), 6.77 (dd, J = 11.0, 3.9 Hz, 4H), 6.61 – 6.55 (m, 6H), 1.35 (s, 36H), 1.12 (s, 18H)； 13C NMR (101 MHz, CDCl 3) δ 143.83, 143.42, 143.24, 141.11, 138.18, 137.62, 136.91, 136.02, 124.28, 124.13, 123.99, 123.80, 122.77, 121.96, 119.99, 118.97, 116.67, 115.99, 115.33, 110.46, 110.40, 109.98, 34.53, 34.21, 31.82, 31.57；MALDI-TOF MS (ESI, m/z) calcd for C 91H 88N 6 [M +]: 1264.71, Found: 1265.915。
由上述检测结果可知，化合物A的结构正确。
以下通过应用实施例说明本发明合成的化合物在器件中作为发光层的应用效果。
实施例一 50 nm 材料A为发光层的有机电致发光器件的制作与性能评价。
50 nm 材料A为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/ A (50 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
50 nm 材料A为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1和图4。
实施例二 100 nm 材料A为发光层的有机电致发光器件的制作与性能评价。
100 nm 材料A为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下。ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/ A (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
100 nm 材料A为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1和图4。
实施例三 150 nm 材料A为发光层的有机电致发光器件的制作与性能评价。
150 nm 材料A为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/ A (150 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
150 nm 材料A为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1和图4。
实施例四 200 nm 材料A为发光层的有机电致发光器件的制作与性能评价。
200 nm 材料A为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下：ITO/HAT-CN (10 nm)/TAPC (40 nm)/mCP (10 nm)/ A (200 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
200 nm 材料A为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见表1和图4。
对比例一。
100 nm的化合物B为发光层（即仅以化合物B为发光层）的有机电致发光器件的制作与性能评价。
化合物B的结构式如下。
Figure 837103dest_path_image005
。
B为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下。ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/ B (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
100nm化合物B为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见图5，开启电压为3.5 V，最大外量子效率为8.4%，电致发光峰值为525 nm。
对比例二。
100 nm的化合物C为发光层（即仅以化合物C为发光层）的有机电致发光器件的制作与性能评价。
化合物C的结构式如下。
Figure 307398dest_path_image006
。
B为发光层的有机电致发光器件的制作步骤如下。
（1)玻璃阳极的预处理：选取带有氧化铟锡（ITO）膜图案作为透明电极的玻璃基板（3×3 mm）；用乙醇将所述玻璃基板洗净后，再用UV-臭氧进行处理，得到预处理的玻璃基板。
（2）真空蒸镀：在所述预处理的玻璃基板上用真空蒸镀法进行各层的真空蒸镀，将处理后的玻璃基板放入真空蒸镀腔内，真空度≤2×10 -4Pa，器件结构如下。ITO/HAT-CN (10 nm)/TAPC (60 nm)/mCP (10 nm)/ C (100 nm)/TMPYPB (45 nm)/LiF (1 nm)/Al (100 nm)；具体各层蒸镀为常规技术。
（3）器件封装：将制作好的有机电致发光器件密封在水氧浓度1 ppm以下的氮气氛围手套箱内，然后使用带有环氧型紫外线固化树脂玻璃质的密封盖盖住上述成膜基板并紫外固化进行密封；具体封装为常规技术。
100nm化合物C为发光层的有机电致发光器件的性能评价。
对所制作的有机电致发光器件施加直流电流，使用积分球来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。器件性能见图6，开启电压为7.0 V，最大外量子效率为14.8%，电致发光峰值为514 nm。
Figure 771878dest_path_image007
。
对比例的化合物制备参考实施例化合物的制备方法。显然，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于所述技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 一种基于热激活延迟荧光材料的超厚非掺杂电致发光器件，以热激活延迟荧光材料为超厚非掺杂发光层，其特征在于：所述热激活延迟荧光材料的化学结构式如下：
    Figure 791790dest_path_image001
    。
  2. 根据权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件，其特征在于，所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件由阳极、空穴注入层、空穴传输层、阻挡层、超厚非掺杂发光层、电子传输层、电子注入层、阴极组成。
  3. 根据权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件，其特征在于，所述超厚非掺杂发光层的厚度为50～200 nm。
  4. 根据权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件，其特征在于，所述超厚非掺杂发光层由所述热激活延迟荧光材料独自组成。
  5. 根据权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件，其特征在于，以2,3,4,5,6-五氟苯腈、3,6-二叔丁基-9H-咔唑和9H-咔唑为原料，反应制备热激活延迟荧光材料。
  6. 根据权利要求5所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件，其特征在于，反应为连续一锅法反应；2,3,4,5,6-五氟苯腈、3,6-二叔丁基-9H-咔唑和9H-咔唑的摩尔比为1∶3～3.5∶2~2.5；所述反应在NaH存在下、氮气保护下进行，反应的温度为室温或加热，反应的时间为12～24 h。
  7. 权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件的制备方法，其特征在于，在阳极上依次真空蒸镀空穴注入层、空穴传输层、阻挡层、超厚非掺杂发光层、电子传输层、电子注入层、阴极，得到所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件。
  8. 电致发光器件的超厚发光层，其特征在于，由权利要求1所述的热激活延迟荧光材料独自组成。
  9. 权利要求8所述电致发光器件的超厚发光层在制备权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件中的应用。
  10. 权利要求1所述基于热激活延迟荧光材料的超厚非掺杂电致发光器件在制备电致发光设备中的应用。
PCT/CN2020/125583 2020-10-30 2020-10-30 基于热激活延迟荧光材料的超厚非掺杂电致发光器件及其制备方法 WO2022088111A1 (zh)

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