WO2020215439A1 - 红色热激活延迟荧光材料及其制备方法、电致发光器件 - Google Patents

红色热激活延迟荧光材料及其制备方法、电致发光器件 Download PDF

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WO2020215439A1
WO2020215439A1 PCT/CN2019/088780 CN2019088780W WO2020215439A1 WO 2020215439 A1 WO2020215439 A1 WO 2020215439A1 CN 2019088780 W CN2019088780 W CN 2019088780W WO 2020215439 A1 WO2020215439 A1 WO 2020215439A1
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thermally activated
activated delayed
delayed fluorescent
fluorescent material
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王彦杰
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the invention relates to the field of display technology, in particular to a red thermally activated delayed fluorescent material, a preparation method thereof, and an electroluminescent device.
  • OLEDs Organic light-emitting diodes
  • OLEDs due to active light emission, large viewing angle, fast response speed, wide temperature adaptation range, low driving voltage, low power consumption, high brightness, simple production process, light and thin, and can
  • the advantages of flexible display and other advantages have shown great application prospects in the field of OLED display and lighting, attracting the attention of scientific researchers and companies.
  • Samsung and LG have implemented OLEDs in mobile phones.
  • the usual luminescent layer material consists of host and guest luminescent materials, and the luminous efficiency and lifetime of luminescent materials are two important indicators of the quality of luminescent materials.
  • Early OLED light-emitting materials were traditional fluorescent materials.
  • the ratio of singlet and triplet excitons is 1:3, while traditional fluorescent materials can only use singlet excitons to emit light. Therefore, traditional fluorescent
  • the OLED theoretical internal quantum efficiency of the material is 25%. Due to the spin-orbit coupling effect of heavy atoms, metal complex phosphorescent materials can achieve 100% utilization of singlet excitons and triplet excitons; and are now also used in red and green OLED display devices .
  • phosphorescent materials usually use heavy metals such as iridium, platinum, osmium and other precious metals, which are not only costly, but also highly toxic. In addition, efficient and long-life phosphorescent metal complex materials are still a great challenge.
  • red thermally activated delayed fluorescent materials TADF
  • ⁇ EST singlet and triplet energy difference
  • PLQY high photoluminescence quantum yield
  • EQE external quantum efficiency
  • the present invention provides a red thermally activated delayed fluorescent material, a preparation method thereof, and an electroluminescent device.
  • the red thermally activated delayed fluorescent molecules have rigid and large planar properties, which can effectively inhibit the reduction of the radiation transition rate due to the energy gap regulation.
  • the carbonyl group in the anthrylimide structure can increase the radiation transition rate of the molecule to obtain high Photoluminescence quantum yield (PLQY).
  • the present invention provides a red thermally activated delayed fluorescent material, including an electron donor and an electron acceptor, wherein the electron acceptor contains an anthrylimide structure.
  • the structure of the red thermally activated delayed fluorescent material is as follows:
  • the group R includes one of an alkyl group, an alkoxy group, and an aromatic group; and the group D is an electron donor.
  • the structure of the electron donor includes one of the following structures:
  • the present invention also provides a preparation method for preparing the red thermally activated delayed fluorescent material.
  • the preparation method includes the following steps: preparing an intermediate including an electron acceptor and an electron acceptor connected to the intermediate. The bromo group on the; the electron acceptor has an anthrylimide structure; the intermediate and the organic acid with the electron donor, the sodium tetrahydrofuran carbon solution are added to the three-necked flask, and carried out with argon Ventilate; add tetrakis(triphenylphosphorus) palladium to the three-necked flask, reflux for 24h at a temperature of 75°C-85°C, and cool to room temperature to obtain a mixed solution; use the mixed solution Dichloromethane was extracted several times, and washed with distilled water after each extraction to obtain an extract; the extract was dried with anhydrous sodium sulfate, filtered, spin-dried, and then column chromatography was performed with 200-300 mesh silica gel and used The elu
  • the step of preparing the intermediate includes adding 7-bromophenylisobenzopyran-1,3-dione, an organic amine with an R group, and ethanol to the application.
  • the group R includes one of an alkyl group, an alkoxy group, and an aromatic group; argon is passed into the Schranke flask, and the Schranke flask is heated under the protection of argon.
  • the reflux reaction is carried out, and the reaction time is 12-24 hours to obtain the first mixed solution; the first mixed solution is extracted with dichloromethane several times, and each extraction is washed with distilled water to obtain the first extract; The first extract is dried with anhydrous sodium sulfate, filtered, and spin-dried, and then column chromatography is performed with 200-300 mesh silica gel and eluted with eluent to obtain the intermediate.
  • the present invention also provides an electroluminescent device, which includes the red thermally activated delayed fluorescent material.
  • the electroluminescent device includes a first electrode; an electron injection layer provided on the first electrode; a hole transport layer provided on the electron injection layer; a light emitting layer , Arranged on the hole transport layer, the material used for the light emitting layer includes the red thermally activated delayed fluorescent material; an electron transport layer, arranged on the light emitting layer; a second electrode, arranged on the electron transport layer.
  • the light-emitting layer further includes 4,4'-N,N'-dicarbazole biphenyl.
  • the first electrode is an anode, and the material used is indium tin oxide; the second electrode is a cathode, and the material used is one of lithium fluoride or aluminum.
  • the material used for the electron injection layer is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • the material used for the electron transport layer is 1,3,5-tris (3-(3-pyridyl) phenyl) benzene; the material used for the hole transport layer is 4,4'-cyclohexyl two [N, N-bis(4-methylphenyl)aniline].
  • the electron acceptor is an anthracene nucleus acceptor, that is, the electron acceptor contains an anthrylimide structure, so that the red thermally activated delayed fluorescent molecule has rigid and large plane characteristics, and can effectively inhibit the
  • the energy gap rule reduces the radiation transition rate, and the carbonyl group in the anthrylimide structure can increase the radiation transition rate of the molecule to obtain high photoluminescence quantum yield (PLQY).
  • the preparation method of the red thermally activated delayed fluorescent material of the present invention can effectively improve the synthesis efficiency.
  • the electroluminescent device of the present invention has the red thermally activated delayed fluorescent material of the present invention. Since the anthracene itself has a P-type delayed fluorescence characteristic in the anthrylimide structure, it can effectively suppress the efficiency roll-off of the device, thereby improving the electrical The efficiency of the electroluminescent device can effectively improve the luminous efficiency.
  • Fig. 1 is a fluorescence spectrum diagram of a red thermally activated delayed fluorescent material prepared by a preparation method in an embodiment of the present invention.
  • Fig. 2 is a structural diagram of an electroluminescent device in an embodiment of the present invention.
  • the red thermally activated delayed fluorescent material of the present invention includes an electron donor and an electron acceptor, wherein the electron acceptor contains an anthrylimide structure.
  • the red thermally activated delayed fluorescent material has the following general structural formula:
  • the group R includes one of an alkyl group, an alkoxy group, and an aromatic group; and the group D is an electron donor.
  • the structure of the electron donor includes one of the following structures;
  • red thermally activated delayed fluorescent material will be further explained below in conjunction with the preparation method of the red thermally activated delayed fluorescent material of the present invention.
  • the preparation of the target compound 1 (a red thermally activated delayed fluorescent material of the present invention) is taken as an example to illustrate the preparation method of the red thermally activated delayed fluorescent material of the present invention in detail.
  • the general structure of the target compound is as follows:
  • the preparation method of the red thermally activated delayed fluorescent material of the present invention includes the following steps:
  • An intermediate is prepared, the intermediate includes an electron acceptor and a bromo group connected to the electron acceptor; the electron acceptor has an anthrylimide structure; and the step of preparing the intermediate includes 7 -Bromophenylisobenzopyran-1,3-dione, organic amine with R group and ethanol are added to Schlenk bottle, said group R includes alkyl group, alkoxy group and aromatic group In one of them, in the preparation of target compound one, the organic amine of the R group is tert-butylamine. Pour argon gas into the Schlenk flask, and heat the Schrank flask under the protection of argon to perform reflux reaction.
  • the reaction time is 12-24 hours to obtain a first mixed solution; Extract with dichloromethane several times, wash with distilled water after each extraction to obtain the first extract; dry the first extract with anhydrous sodium sulfate, filter, spin dry, and then use 200-300 mesh silica gel Column chromatography and elution with eluent to obtain the intermediate: 7-bromo-2-tert-butyl-diphenylisoquinoline-1,3-dione.
  • the organic acid with the electron donor is 4-(9,9-dimethylacridine)-phenylboronic acid.
  • Tetrakis(triphenylphosphorus) palladium was added to the three-necked flask, and the reaction was refluxed at a temperature of 75° C.-85° C. for 24 hours, and a mixed solution was obtained after cooling to room temperature.
  • the mixed solution is extracted with dichloromethane several times, and washed with distilled water after each extraction to obtain an extract.
  • the extract is dried with anhydrous sodium sulfate, filtered, and spin-dried, and then column chromatography is performed with 200-300 mesh silica gel and eluted with eluent to obtain the target compound one, which is a red color of the present invention.
  • the thermally activated delayed fluorescent material has a yield of 85%.
  • target compound two a red thermally activated delayed fluorescent material of the present invention
  • preparation method of the red thermally activated delayed fluorescent material of the present invention is described in detail.
  • the general structure of the target compound is as follows:
  • the preparation method of the red thermally activated delayed fluorescent material of the present invention includes the following steps:
  • An intermediate is prepared, the intermediate includes an electron acceptor and a bromo group connected to the electron acceptor; the electron acceptor has an anthrylimide structure; and the step of preparing the intermediate includes 7 -Bromophenylisobenzopyran-1,3-dione, organic amine with R group and ethanol are added to Schlenk bottle, said group R includes alkyl group, alkoxy group and aromatic group In one of them, in the preparation of the second target compound, the organic amine of the R group is p-tert-butylaniline. Pour argon gas into the Schlenk flask, and heat the Schrank flask under the protection of argon to perform reflux reaction.
  • the reaction time is 12-24 hours to obtain a first mixed solution; Extract with dichloromethane several times, wash with distilled water after each extraction to obtain the first extract; dry the first extract with anhydrous sodium sulfate, filter, spin dry, and then use 200-300 mesh silica gel Column chromatography and elution with eluent to obtain the intermediate: 7-bromo-2-tert-butyl-diphenylisoquinoline-1,3-dione.
  • the organic acid with the electron donor is 4-(9,9-dimethylacridine)-phenylboronic acid.
  • Tetrakis(triphenylphosphorus) palladium was added to the three-necked flask, and the reaction was refluxed at a temperature of 75° C.-85° C. for 24 hours, and a mixed solution was obtained after cooling to room temperature.
  • the mixed solution is extracted with dichloromethane several times, and washed with distilled water after each extraction to obtain an extract.
  • the extract is dried with anhydrous sodium sulfate, filtered, and spin-dried, and then column chromatography is performed with 200-300 mesh silica gel and eluted with eluent to obtain the target compound one, which is a red color of the present invention.
  • Thermally activated delayed fluorescent material with a yield of 88%
  • the red thermally activated delayed fluorescent material By preparing the red thermally activated delayed fluorescent material by the preparation method of this embodiment, the red thermally activated delayed fluorescent material can be effectively synthesized, and the synthesis efficiency can be improved.
  • the red thermally activated delayed fluorescent material obtained by the preparation method of this embodiment is subjected to spectral experiments and photophysical data detection . Obtain the fluorescence spectrum shown in Figure 1 and the photophysical data shown in Table 1.
  • Table 1 shows the photophysical data of the red thermally activated delayed fluorescent material of the present invention.
  • the effective wavelength range of the target compound 1 of the present invention is between 680-800 nm, and the effective wavelength range of the target compound 2 is between 700-850 nm. Therefore, the emission spectrum of the molecule can be adjusted within this range. It can be seen from Table 1 that the red thermally activated delayed fluorescent material of the present invention has a smaller minimum singlet state and triplet energy difference ( ⁇ E ST ).
  • the present invention also provides an electroluminescent device, which includes the red thermally activated delayed fluorescent material.
  • the electroluminescent device includes a first electrode 1, an electron injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a second electrode 6.
  • the electron injection layer 2 is provided on the first electrode 1;
  • the hole transport layer 3 is provided on the electron injection layer 2;
  • the light emitting layer 4 is provided on the hole transport layer 3 ,
  • the material used for the light-emitting layer 4 includes the red thermally activated delayed fluorescent material and 4,4'-N,N'-dicarbazole biphenyl, 4,4'-N,N'-dicarbazole biphenyl is The host molecule is doped with the red thermally activated delayed fluorescent material;
  • the electron transport layer 5 is provided on the light-emitting layer 4;
  • the second electrode 6 is provided on the electron transport layer 5.
  • the first electrode 1 is an anode, and the material used is indium tin oxide; the second electrode 6 is a cathode, and the material used is one of lithium fluoride or aluminum.
  • the material used for the electron transport layer 5 is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene; the material used for the hole transport layer 3 is 4,4'-cyclohexylbis[N ,N-bis(4-methylphenyl)aniline], the material used for the electron injection layer 2 is 2,3,6,7,10,11-hexacyano-1,4,5,8,9, 12-hexaazatriphenylene.
  • Table 2 is a performance data table of the electroluminescent device 10 using target compound one or using target compound two.
  • the red thermally activated delayed fluorescent material is used in the light-emitting layer 4 to effectively manufacture a red electroluminescent device and improve the luminous efficiency of the red electroluminescent device.

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Abstract

一种红色热激活延迟荧光材料及其制备方法、电致发光器件。红色热激活延迟荧光材料包括电子给体和电子受体，其中，电子受体中含有蒽基酰亚胺结构。电子受体中的蒽基酰亚胺结构，使得红色热激活延迟荧光分子具有刚性和大平面特性，能够有效抑制由于能隙规则导致的辐射跃迁速率的降低，同时蒽基酰亚胺结构中的羰基能够增加分子的辐射跃迁速率，以获得高的光致发光量子产率(PLQY)。

Description

红色热激活延迟荧光材料及其制备方法、电致发光器件 技术领域
本发明涉及显示技术领域，具体为一种红色热激活延迟荧光材料及其制备方法、电致发光器件。
背景技术
有机发光二极管(organic lighting-emitting diodes,OLEDs)，由于主动发光、可视角度大、相应速度快、温度适应范围宽、驱动电压低、功耗小、亮度大、生产工艺简单、轻薄、且可以柔性显示等优点，在OLED显示和照明领域表现出巨大的应用前景，吸引了科研工作者和公司的关注。目前，三星、LG已经实现OLEDs应用在手机上。在OLED中，发光层材料的优劣是OLED能否产业化起决定作用。通常的发光层材料由主体和客体发光材料，而发光材料的发光效率和寿命是发光材料好坏的两个重要指标。早期的OLED发光材料为传统荧光材料，由于在OLED显示装置中，单重态和三重态的激子比例为1:3，而传统荧光材料只能利用单重态激子发光，因此，传统荧光材料的OLED理论内量子效率为25％。金属配合物磷光材料由于重原子的自旋轨道耦合效应，使得其能够实现单重态激子和三重态激子的100％利用率；并且现在也已经用在红光和绿光OLED显示装置上。但是，磷光材料通常要使用重金属铱、铂、锇等贵重金属，不仅成本高，而且毒性较 大。此外，高效、长寿命的磷光金属配合物材料仍旧是极大的挑战。
对于红色热激活延迟荧光材料(TADF)，较小的最低单重态和三重能级差(ΔEST)以及高的光致发光量子产率(PLQY)是制备高效率OLED的必要条件。目前，绿光和天蓝光红色热激活延迟荧光材料已经获得超过30％的外量子效率(EQE)；但是红光及深红色热激活延迟荧光材料由于能隙规则(Energy gap law)，无法获得优异的器件性能。
技术问题
为解决上述技术问题：本发明提供一种红色热激活延迟荧光材料及其制备方法、电致发光器件，电子受体为蒽核受体，即电子受体中含有蒽基酰亚胺结构，使得红色热激活延迟荧光分子具有刚性和大平面特性，能够有效抑制由于能隙规则导致的辐射跃迁速率的降低，同时蒽基酰亚胺结构中的羰基能够增加分子的辐射跃迁速率，以获得高的光致发光量子产率(PLQY)。
技术解决方案
解决上述问题的技术方案是：本发明提供一种红色热激活延迟荧光材料，包括电子给体和电子受体，其中，所述电子受体中含有蒽基酰亚胺结构。
在本发明一实施例中，所述的红色热激活延迟荧光材料，其结构 通式如下：
Figure PCTCN2019088780-appb-000001
所述结构通式中，基团R包括烷基、烷氧基、芳香基中的一种；基团D为电子给体。
在本发明一实施例中，所述电子给体的结构包括以下结构中的一种；
Figure PCTCN2019088780-appb-000002
Figure PCTCN2019088780-appb-000003
本发明还提供了一种制备方法，用来制作所述的红色热激活延迟荧光材料，所述制备方法包括以下步骤：制备中间体，所述中间体中包括电子受体以及连接在电子受体上的溴基；所述电子受体中具有蒽基酰亚胺结构；将所述中间体以及带有电子给体的有机酸、四氢呋喃碳的酸钠水溶液加入至三口烧瓶中，并用氩气进行抽换气；将四(三苯基磷)合钯加入至所述三口烧瓶中，在温度为75℃-85℃条件下回流反应24h，冷却至室温后得到混合溶液；将所述混合溶液用二氯甲 烷萃取多次，每次萃取后用蒸馏水进行水洗，得到萃取液；将所述萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述红色热激活延迟荧光材料。
在本发明一实施例中，在制备所述中间体步骤中，包括将7-溴苯基异苯并吡喃-1,3-二酮、带有R基团的有机胺以及乙醇加入到施兰克瓶中，所述基团R包括烷基、烷氧基、芳香基中的一种；向所述施兰克瓶中通入氩气，在氩气保护下加热所述施兰克瓶进行回流反应，反应时间为12-24小时，得到第一混合溶液；将所述第一混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到第一萃取液；将所述第一萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述中间体。
本发明还提供了一种电致发光器件，包括所述的红色热激活延迟荧光材料。
在本发明一实施例中，所述的电致发光器件，包括第一电极；电子注入层，设于所述第一电极上；空穴传输层，设于所述电子注入层上；发光层，设于所述空穴传输层上，所述发光层所用材料包括所述红色热激活延迟荧光材料；电子传输层，设于发光层上；第二电极，设于所述电子传输层上。
在本发明一实施例中，所述发光层中还包括4,4’-N,N’-二咔唑联苯。
在本发明一实施例中，所述第一电极为阳极，其所用材料为氧化铟锡；所述第二电极为阴极，其所用材料为氟化锂或铝中的一种。 在本发明一实施例中，所述电子注入层所用材料为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲；所述电子传输层所用材料为1,3,5-三(3-(3-吡啶基)苯基)苯；所述空穴传输层所用材料为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]。
有益效果
本发明的红色热激活延迟荧光材料，电子受体为蒽核受体，即电子受体中含有蒽基酰亚胺结构，使得红色热激活延迟荧光分子具有刚性和大平面特性，能够有效抑制由于能隙规则导致的辐射跃迁速率的降低，同时蒽基酰亚胺结构中的羰基能够增加分子的辐射跃迁速率，以获得高的光致发光量子产率(PLQY)。本发明的红色热激活延迟荧光材料的制备方法，能够有效的提高了合成效率。本发明的电致发光器件，其具有本发明的红色热激活延迟荧光材料，由于蒽基酰亚胺结构中，蒽本身具有P型延迟荧光特性，能够有效抑制器件的效率滚降，从而提高电致发光器件的效率，能够有效的提高发光效率。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
下面结合附图和实施例对本发明作进一步解释。
图1是本发明实施例中的制备方法制得的红色热激活延迟荧光材料的荧光光谱图。
图2是本发明实施例中电致发光器件结构图。
附图标记：
10电致发光器件；
1第一电极；                  2电子注入层；
3空穴传输层；                4发光层；
5电子传输层；                6第二电极。
本发明的实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
以下实施例的说明是参考附加的图式，用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语，例如「上」、「下」、「前」、「后」、「左」、「右」、「顶」、「底」等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本发明，而非用以限制本发明。
本发明的红色热激活延迟荧光材料，包括电子给体和电子受体，其中，所述电子受体中含有蒽基酰亚胺结构。所述红色热激活延迟荧光材料具有以下结构通式：
Figure PCTCN2019088780-appb-000004
所述结构通式中，基团R包括烷基、烷氧基、芳香基中的一种；基团D为电子给体。
所述电子给体的结构包括以下结构中的一种；
Figure PCTCN2019088780-appb-000005
Figure PCTCN2019088780-appb-000006
为了更加清楚的解释本发明，下面结合本发明的红色热激活延迟荧光材料制备方法对所述红色热激活延迟荧光材料进行进一步解释。
在本发明一实施例中，以制备目标化合物一(本发明的一种红色热激活延迟荧光材料)为例，详细说明本发明的红色热激活延迟荧光材料制备方法。其中目标化合物的结构通式如下：
Figure PCTCN2019088780-appb-000007
目标化合物一的合成路线如下所示：
Figure PCTCN2019088780-appb-000008
参见所述目标化合物一的合成路线，本发明的红色热激活延迟荧光材料制备方法包括以下步骤：
制备中间体，所述中间体中包括电子受体以及连接在电子受体上的溴基；所述电子受体中具有蒽基酰亚胺结构；在制备所述中间体步骤中，包括将7-溴苯基异苯并吡喃-1,3-二酮、带有R基团的有机胺 以及乙醇加入到施兰克瓶中，所述基团R包括烷基、烷氧基、芳香基中的一种，在制备目标化合物一中，所述R基团的有机胺选用叔丁基胺。向所述施兰克瓶中通入氩气，在氩气保护下加热所述施兰克瓶进行回流反应，反应时间为12-24小时，得到第一混合溶液；将所述第一混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到第一萃取液；将所述第一萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述中间体：7-溴-2-叔丁基-二苯异喹啉-1,3-二酮。
所述中间体的结构通式如下：
Figure PCTCN2019088780-appb-000009
将所述中间体以及带有电子给体的有机酸、四氢呋喃碳的酸钠水溶液加入至三口烧瓶中，并用氩气进行抽换气。在制备目标化合物一中，带有电子给体的有机酸选用4-(9,9-二甲基吖啶)-苯硼酸。
将四(三苯基磷)合钯加入至所述三口烧瓶中，在温度为75℃-85℃条件下回流反应24h，冷却至室温后得到混合溶液。
将所述混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到萃取液。
将所述萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述目标化合物一，即本发明的一种红色热激活延迟荧光材料，其产率为85％。
在本发明另一实施例中，以制备目标化合物二(本发明的一种红色热激活延迟荧光材料)为例，详细说明本发明的红色热激活延迟荧光材料制备方法。其中目标化合物的结构通式如下：
Figure PCTCN2019088780-appb-000010
目标化合物一的合成路线如下所示：
Figure PCTCN2019088780-appb-000011
参见所述目标化合物一的合成路线，本发明的红色热激活延迟荧光材料制备方法包括以下步骤：
制备中间体，所述中间体中包括电子受体以及连接在电子受体上的溴基；所述电子受体中具有蒽基酰亚胺结构；在制备所述中间体步骤中，包括将7-溴苯基异苯并吡喃-1,3-二酮、带有R基团的有机胺以及乙醇加入到施兰克瓶中，所述基团R包括烷基、烷氧基、芳香基中的一种，在制备目标化合物二中，所述R基团的有机胺选用对叔丁基苯胺。向所述施兰克瓶中通入氩气，在氩气保护下加热所述施兰克瓶进行回流反应，反应时间为12-24小时，得到第一混合溶液；将所述第一混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到第一萃取液；将所述第一萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述中 间体：7-溴-2-叔丁基-二苯异喹啉-1,3-二酮。
所述中间体的结构通式如下：
Figure PCTCN2019088780-appb-000012
将所述中间体以及带有电子给体的有机酸、四氢呋喃碳的酸钠水溶液加入至三口烧瓶中，并用氩气进行抽换气。在制备目标化合物一中，带有电子给体的有机酸选用4-(9,9-二甲基吖啶)-苯硼酸。
将四(三苯基磷)合钯加入至所述三口烧瓶中，在温度为75℃-85℃条件下回流反应24h，冷却至室温后得到混合溶液。
将所述混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到萃取液。
将所述萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述目标化合物一，即本发明的一种红色热激活延迟荧光材料，其产率为88％
通过本实施例的制备方法制备红色热激活延迟荧光材料，能够有效合成红色热激活延迟荧光材料，同时能够提高合成效率。
为了验证本发明的红色热激活延迟荧光材料的特性是否满足电致发光器件的要求，因此本实施例中将通过本实施例的制备方法得到的红色热激活延迟荧光材料进行光谱实验和光物理数据检测。得到如图1所示的荧光光谱图以及如表1所示的光物理数据。
表1为本发明的红色热激活延迟荧光材料的光物理数据。
PL Peak(nm) S 1(eV) T 1(eV) E ST(eV) PLQY(％)
目标化合物一 721 2.35 2.16 0.19 75
目标化合物二 763 2.11 1.96 0.15 68
由图1可知，本发明的目标化合物一的有效波长范围在680-800nm之间，目标化合物二的有效波长范围在700-850nm之间。因此，可以在此范围内调节分子的发光光谱。由表1可知，本发明的红色热激活延迟荧光材料具有较小的最低单重态和三重能级差(ΔE ST)。
如图2所示，本发明还提供了一种电致发光器件，包括所述的红色热激活延迟荧光材料。
具体的，所述的电致发光器件包括第一电极1、电子注入层2、空穴传输层3、发光层4、电子传输层5、第二电极6。其中，所述电子注入层2设于所述第一电极1上；所述空穴传输层3设于所述电子注入层2上；所述发光层4设于所述空穴传输层3上，所述发光层4所用材料包括所述红色热激活延迟荧光材料以及4,4’-N,N’-二咔唑联苯，4,4’-N,N’-二咔唑联苯为主体分子，其中掺杂所述红色热激活延迟荧光材料；所述电子传输层5设于所述发光层4上；所述第二电极6设于所述电子传输层5上。
本实施例中，所述第一电极1为阳极，其所用材料为氧化铟锡；所述第二电极6为阴极，其所用材料为氟化锂或铝中的一种。所述电子传输层5所用材料为1,3,5-三(3-(3-吡啶基)苯基)苯；所述空穴传输层3所用材料为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]，所述电子注入层2所用材料为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲。
表2为采用目标化合物一或者采用目标化合物二的电致发光器件10的性能数据表。
Figure PCTCN2019088780-appb-000013
本发明的电致发光器件10，在发光层4采用所述的红色热激活延迟荧光材料，有效的制作出红色电致发光器件，提高了红色电致发光器件的发光效率。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种红色热激活延迟荧光材料，其包括电子给体和电子受体，其中，所述电子受体中含有蒽基酰亚胺结构。
  2. 根据权利要求1所述的红色热激活延迟荧光材料，其中，其结构通式如下：
    Figure PCTCN2019088780-appb-100001
    所述结构通式中，基团R包括烷基、烷氧基、芳香基中的一种；基团D为电子给体。
  3. 根据权利要求1所述的红色热激活延迟荧光材料，其中，所述电子给体的结构包括以下结构中的一种；
    Figure PCTCN2019088780-appb-100002
    Figure PCTCN2019088780-appb-100003
  4. 一种制备方法，用来制作如权利要求1所述的红色热激活延迟荧光材料，其中，所述制备方法包括以下步骤：
    制备中间体，所述中间体中包括电子受体以及连接在电子受体上的溴基；所述电子受体中具有蒽基酰亚胺结构；
    将所述中间体以及带有电子给体的有机酸、四氢呋喃碳的酸钠水溶液加入至三口烧瓶中，并用氩气进行抽换气；
    将四(三苯基磷)合钯加入至所述三口烧瓶中，在温度为75℃-85℃条件下回流反应24h，冷却至室温后得到混合溶液；
    将所述混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到萃取液；
    将所述萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述红色热激活延迟荧光材料。
  5. 根据权利要求4所述的制备方法，其中，
    在制备所述中间体步骤中，包括
    将7-溴苯基异苯并吡喃-1,3-二酮、带有R基团的有机胺以及乙醇加入到施兰克瓶中，所述基团R包括烷基、烷氧基、芳香基中的一种；向所述施兰克瓶中通入氩气，在氩气保护下加热所述施兰克瓶进行回流反应，反应时间为12-24小时，得到第一混合溶液；
    将所述第一混合溶液用二氯甲烷萃取多次，每次萃取后用蒸馏水进行水洗，得到第一萃取液；
    将所述第一萃取液用无水硫酸钠干燥，过滤，旋干，之后用200-300目的硅胶进行柱层析，并用淋洗液淋洗，得到所述中间体。
  6. 一种电致发光器件，其包括如权利要求1所述的红色热激活延迟荧光材料。
  7. 根据权利要求6所述的电致发光器件，其包括
    第一电极；
    电子注入层，设于所述第一电极上；
    空穴传输层，设于所述电子注入层上；
    发光层，设于所述空穴传输层上，所述发光层所用材料包括所述红色热激活延迟荧光材料；
    电子传输层，设于发光层上；
    第二电极，设于所述电子传输层上。
  8. 根据权利要求7所述的电致发光器件，其中，所述发光层中还包括4,4’-N,N’-二咔唑联苯。
  9. 根据权利要求7所述的电致发光器件，其中，所述第一电极为阳极，其所用材料为氧化铟锡；所述第二电极为阴极，其所用材料为氟化锂或铝中的一种。
  10. 根据权利要求8所述的电致发光器件，其中，
    所述电子注入层所用材料为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲；
    所述电子传输层所用材料为1,3,5-三(3-(3-吡啶基)苯基)苯；
    所述空穴传输层所用材料为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]。
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