CN112480154B - 一种手性热活化延迟荧光材料及其圆偏振电致发光器件 - Google Patents
一种手性热活化延迟荧光材料及其圆偏振电致发光器件 Download PDFInfo
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- CN112480154B CN112480154B CN202011348316.1A CN202011348316A CN112480154B CN 112480154 B CN112480154 B CN 112480154B CN 202011348316 A CN202011348316 A CN 202011348316A CN 112480154 B CN112480154 B CN 112480154B
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Abstract
本发明提供一种手性热活化延迟荧光材料及其圆偏振电致发光器件，所述热活化延迟荧光材料具有以下结构:
本发明提供的手性热活化延迟荧光材料的分子结构为大芳香稠环结构的共振分子，易于实现窄带发射。本发明还公开了上述手性TADF有机发光材料在有机电致圆偏振发光器件中的应用。本发明的手性TADF有机发光材料具有高的荧光量子产率、窄带发射光谱和圆偏振光性质，可用于制备高效的有机电致发光器件。
Description
技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种手性热活化延迟荧光材料及其圆偏振电致发光器件。
背景技术
有机发光二极管(organic light-emitting diodes，OLED)，具有自发光、响应时间短、使用温度范围宽、驱动电压低以及能耗低、轻质、柔性等特点，在新一代平板显示技术、固态照明、柔性显示、透明显示等方面具有广阔的应用前景，因此倍受国内外科技界和产业界关注。
有机发光材料根据其发光原理大致分为三种，传统荧光材料、磷光材料以及热活化延迟荧光(TADF)材料。传统荧光材料具有稳定性好、成本低的优势，但是其器件效率较低；磷光材料具有器件效率高的优势，但是其蓝光器件寿命短，且贵金属的引入提高了材料成本。TADF材料自2009年日本九州大学的Adachi教授首次报道以来，引发了科研界和产业界的广泛关注。从热活化延迟荧光材料的设计理念来看，主要有两种，电荷转移态TADF(CT-TADF)材料和多重共振式TADF(MR-TADF)材料。两者的主要区别是CT-TADF材料的发射半峰宽比较宽，色纯度较差，而后者采用稠环芳烃骨架限制分子转动，将缺电子的B原子(受体)与富电子的N原子(给体)包含在同一核心结构中，得到发射光谱半峰宽小于30nm(已达到量子点材料的半峰宽)的纯蓝光MR-TADF分子DABNA-1和DABNA-2(Adv.Mater.2016,28,2777)。MR-TADF发光材料的色纯度高，在显示应用上有较大的优势。
与此同时，当前研究的TADF材料几乎全部都是非手性发光材料，不具备圆偏振发光性质。应用过程中，在引入四分之一波长片与偏振片后，虽然可以提高器件开/关状态下的发光对比度，但也会造成出光效率减半。使用手性分子材料作为发光层，材料发出的圆偏振光可以有效透过偏振片与四分之一波长片，避免了有机电致发光二极管(OLED)的效率损失。结合高效的内转换与外提取过程，圆偏振TADF材料制备的OLED器件理论上可以获得理想的出光效率。因此，开发具有圆偏振发光性质的TADF材料具有重要意义。
现阶段，圆偏振发光领域的研究主要集中在手性分子材料的构筑、调控以及组装研究。但这些圆偏振发光的手性分子具有TADF性质的较少，能够实现超窄发射的几乎没有报道。
发明内容
鉴于现有技术的不足，本发明的目的在于提供一种色纯度高的手性热活化延迟荧光材料及其圆偏振电致发光器件，旨在解决色纯度高的有机电致发光器件效率较低的问题。
本发明的技术方案如下：
一种手性热活化延迟荧光材料，其特征在于，其结构式如式(1)所示：
优选地，R1-R11各自独立地选自氢、氘、卤素、氰基、脒基、肼、腙、取代或未取代的C1-C60的烷基、取代或未取代的C2-C60的烯基、取代或未取代的C1-C60的烷胺基、取代或未取代的C2-C60的烯胺基、取代或未取代的C1-C60的烷氧基、取代或未取代的C2-C60的烯氧基、取代或未取代的C4-C60的芳基、取代或未取代的C3-C60的杂芳基、取代或未取代的C4-C60的芳氧基、取代或未取代的C4-C60的芳香胺基、取代或未取代的C4-C60的硫代芳氧基、取代或未取代的C4-C60的芳硼基，或者R1-R11中任意相邻的两个至四个基团连接形成一组或多组环A，所述环A选自取代或未取代的3-7元的碳环、取代或未取代的3-7元的杂环、取代或未取代的C4-C60的芳基或取代或未取代的C3-C60的杂芳基，所述碳环为饱和或不饱和环，所述杂环为饱和或不饱和环；
优选地，X1和X2各自独立地选自甲基、三氟甲基、卤素、氰基、取代或未取代的C1-C60的烷基、取代或未取代的C2-C60的烯基、取代或未取代的C1-C60的烷胺基、取代或未取代的C2-C60的烯胺基、取代或未取代的C1-C60的烷氧基、取代或未取代的C2-C60的烯氧基、取代或未取代的C4-C60的芳基、取代或未取代的C3-C60的杂芳基、取代或未取代的C4-C60的芳氧基、取代或未取代的C4-C60的芳香胺基、取代或未取代的C4-C60的硫代芳氧基、取代或未取代的C4-C60的芳硼基，取代或为取代的C6-C60的芳香环基、取代或未代的C3-C60的芳杂环基的一种；所述Y1和Y2各自独立的选自-O-、-S-、-S＝O-、-SO2-、-C(R12R13)-、-Si(R12R13)-、-Ge(R12R13)-、-N(R12)-、-P(R12)-、-P＝O(R12)-或不成键中的一种；
优选地，Z1与Z2各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代的C6-C60的芳香环基、未取代的C6-C60的芳香环基、取代的C3-C60的芳杂环基或未取代的C3-C60的芳杂环基的一种方式相连成环，或者独立的选自-O-、-S-、-S＝O-、-SO2-、-C(R12R13)-、-Si(R12R13)-、-Ge(R12R13)-、-N(R12)-、-P(R12)-、-P＝O(R12)-或不成键中的一种。R12和R13各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代或未取代的C6-C60芳香环基及取代或未取代的C3-C60芳杂环基中的一种；
优选地，R12和R13各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代或未取代的C6-C60芳香环基及取代或未取代的C3-C60芳杂环基中的一种；其中，虚线代表镜面。
优选地，所述手性热活化延迟荧光材料为如下化合物中的任何一种：
其中，虚线代表镜面。
按照本发明的另一方面，提供了一种电致发光器件，包括发光层，所述发光层包括本发明所述的热活化延迟荧光材料。
有益效果：本发明提供的手性热活化延迟荧光材料的分子结构为多重共振的大稠环构型，其中缺电子的B和富电子的N或者O形成共振，大稠环结构抑制了分子振动，能够同时实现超窄发射和热活化延迟荧光性质。在此基础上，引入手性基团，形成具有手性的超窄发射TADF分子，在电致发光器件中表现出电致圆偏振发光性质，能够极大提升器件效率，且色纯度高。
附图说明
图1是化合物1的室温荧光和低温磷光光谱；
图2是化合物22的室温荧光和低温磷光光谱；
图3是化合物61的室温荧光和低温磷光光谱；
图4是化合物16的寿命衰减曲线；
图5是化合物22的寿命衰减曲线；
图6是化合物61的寿命衰减曲线；
图7是化合物22的电致圆偏振图；
图8是化合物61和128的寿命衰减曲线；
图9是根据本发明的实施例提供的OLED器件的结构示意图。
具体实施方式
本发明提供一种手性热活化延迟荧光材料及其圆偏振电致发光器件，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
以下为具体实施例：
实施例1
化合物1的制备方法包括以下步骤：
1)、中间体1-1的制备反应式如下：
准备一个50mL干燥的双口圆底烧瓶，中间体(1)(2mmol)，中间体(2)(1mmol)，醋酸钯(0.1mmol)，三叔丁基膦四氟硼酸盐(0.2mmol.)，叔丁醇钠(2.5mmol.)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥甲苯(20mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物1-1，HPLC纯度99.2％，产率：90％。MS(MALDI-TOF):m/z 559.36[M+H+]。
2)、化合物1的合成
在-40℃的氩气氛围下，向盛有中间体1-1(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(20:1))来对剩余粗产物进行精制得到浅黄色固体，即获得化合物1，HPLC纯度99.3％，产率30％。MS(MALDI-TOF):m/z 533.56[M+H+]。
实施例2
化合物16的制备方法包括以下步骤：
1)、中间体16-1的制备反应式如下：
准备一个50mL干燥的双口圆底烧瓶，中间体(3)(2mmol)，中间体(2)(1mmol)，醋酸钯(0.1mmol)，三叔丁基膦四氟硼酸盐(0.2mmol.)，叔丁醇钠(2.5mmol.)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥甲苯(20mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物16-1，HPLC纯度99.2％，产率：65％。MS(MALDI-TOF):m/z 659.78.[M+H+]。
2)、化合物16的制备反应式如下：
在-40℃的氩气氛围下，向盛有中间体16-1(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(20:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物16，HPLC纯度99.5％，产率15％。MS(MALDI-TOF):m/z 633.34[M+H+]。
实施例3
化合物22的制备方法包括以下步骤：
1)、中间体22-1的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(4)(2mmol)，中间体(5)(1mmol)，CsCO3(2.5mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物22-1，HPLC纯度99.8％，产率：86％。MS(MALDI-TOF):m/z747.52.[M+H+]。
2)、化合物22的制备反应式如下：
在-40℃的氩气氛围下，向盛有中间体22-1(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(15:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物22，亮黄色粉末，HPLC纯度99.0％，产率13％。MS(MALDI-TOF):m/z 721.63[M+H+]。
实施例4
化合物61的制备方法包括以下步骤：
1)、化合物61-1的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(6)(2mmol)，中间体(7)(1mmol)，CsCO3(2.5mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物61-1，HPLC纯度99.8％，产率：74％。MS(MALDI-TOF):m/z772.41.[M+H+]。
2)、化合物61的制备反应式如下：
在-40℃的氩气氛围下，向盛有中间体61-1(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(15:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物61，亮黄色粉末，HPLC纯度99.3％，产率14％。MS(MALDI-TOF):m/z 746.69[M+H+]。
实施例5
化合物70的制备方法包括以下步骤：
1)、中间体70-1的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(8)(1mmol)，中间体(9)(1mmol)，CsCO3(1.1mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物70-1，HPLC纯度99.0％，产率：54％。MS(MALDI-TOF):m/z509.86.[M+H+]。
2)、中间体70-2的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(70-1)(1mmol)，中间体(4)(1mmol)，CsCO3(1.1mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物70-2，HPLC纯度99.0％，产率：41％。MS(MALDI-TOF):m/z809.62.[M+H+]。
3)、中间体70-3的制备反应式如下：
在-40℃的氩气氛围下，向装有中间体70-2(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(15:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物70-3，亮黄色粉末，HPLC纯度99.4％，产率38％。MS(MALDI-TOF):m/z 737.89[M+H+]。
4)、化合物70的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(70-3)(1mmol)，CuCN(3mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下150℃搅拌24h。反应液冷却至室温后，加水，固体析出，二氯甲烷溶解，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到橙色粉末，即化合物70，HPLC纯度99.2％，产率：31％。MS(MALDI-TOF):m/z 684.56.[M+H+]。
实施例6
化合物128的制备方法包括以下步骤：
1)、中间体128-1的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(10)(1mmol)，中间体(4)(1mmol)，CsCO3(1.1mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物128-1，HPLC纯度99.3％，产率：55％。MS(MALDI-TOF):m/z368.54.[M+H+]。
2)、中间体128-2的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(128-1)(1mmol)，中间体(12)(1mmol)，CsCO3(1.1mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物128-2，HPLC纯度99.3％，产率：43％。MS(MALDI-TOF):m/z 695.87.[M+H+]。
3)、化合物128的制备反应式如下：
在-40℃的氩气氛围下，向装有中间体128-2(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(15:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物128，亮黄色粉末，HPLC纯度99.4％，产率29％。MS(MALDI-TOF):m/z 625.62[M+H+]。
实施例7
化合物152的制备方法包括以下步骤：
1)、中间体152-1的制备反应式如下：
准备一个100mL干燥的双口圆底烧瓶，中间体(13)(1mmol)，中间体(14)(2.1mmol)，CsCO3(2.2mmol)加入烧瓶中，连上冷凝管，除气并通入氮气，反复三次。加入干燥DMF(50mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到白色固体，即化合物152-1，HPLC纯度99.6％，产率：62％。MS(MALDI-TOF):m/z 875.43.[M+H+]。
2)、化合物152的制备反应式如下：
在-40℃的氩气氛围下，向装有中间体152-1(3mmol)的叔丁基苯(150ml)的耐压瓶中逐滴加入1.5M的叔丁基锂戊烷溶液(6.6mmol)，并缓慢升温至60℃搅拌5小时。随后将沸点低于叔丁基苯的成分减压馏去。冷却至-40℃并添加三溴化硼(7.5mmol)，缓慢升温至室温后搅拌1小时。再次冷却反应体系至0℃并添加N,N-二异丙基乙胺(15mmol)，缓慢升温至室温并密封，继续升温至180℃搅拌24小时。之后将反应液冷却至室温，滴加甲醇淬灭，并将溶剂减压馏去。进一步利用硅胶柱层析法(展开剂：正己烷/二氯甲烷＝(15:1))来对剩余粗产物进行精制得到黄色固体，即获得化合物152，亮黄色粉末，HPLC纯度99.0％，产率10％。MS(MALDI-TOF):m/z 805.91[M+H+]。
本发明的上述手性超窄发射热活化延迟荧光材料可适用于OLED器件中的发光层。以下结合附图9的器件结构，通过化合物1、16、22、61、70、128和152这7个实施例详细说明本发明的热活化延迟材料在OLED器件中作为发光层材料的应用效果。
图1-3分别为化合物1、22和61的室温荧光和低温磷光光谱，图3-6分别为化合物16、22和61的寿命衰减图，图7为化合物22的电致圆偏振发光曲线；图8为化合物61和128的电致圆偏振发光曲线；图9为七个实施例的器件结构示意图。
本发明提供的电致发光器件，参照附图9所示结构，可包括导电玻璃衬底1(ITO)、空穴注入层2(12-六氮杂苯并菲，HAT-CN)、空穴传输层3(4,4’-环己基二[N,N-二(4-甲基苯基)苯胺]，TAPC)、电子阻挡层4(1,3-双(咔唑-9-基)苯，mCP)、发光层5(本发明具有手性的超窄发射的热活化延迟荧光的化合物掺入主体材料的混合物)、空穴阻挡层6(二[2-((氧代)二苯基膦基)苯基]醚，DPEPO)、电子传输层7(3',1”-三联苯-3,3”-二基二吡啶，TmPyPB)、电子注入层8(8-羟基喹啉-锂，Liq)、阴极层9(Al)。
其中HAT-CN、mCP、DPEPO、TmPyPB、Liq、TAPC的结构式分别如下：
参照附图6所示结构，制造OLED器件，具体步骤为：将镀有氧化铟锡(ITO)的玻璃基板分别用去离子水、丙酮、异丙醇超声洗涤30分钟，紫外线臭氧处理15分钟后，将玻璃基板传送至真空沉积室中；旋涂、蒸镀各有机层及阴极铝层；将该器件从沉积室传送至手套箱中进行封装。
实施例8-14的器件具体结构如下：
ITO/HAT-CN(5nm)/TAPC(30nm)/mCP(10nm)/主体(mCP或mCBP或mCBPCN):1-15wt.％掺杂客体(化合物1或16或22或61或70或128或152)(20-25nm)/DPEPO(10nm)/TmPyPB(30nm)/Liq(1.5nm)/Al(100nm)。
器件的亮度、发光效率、EQE(外量子效率)由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400Sourcemeter、Keithley 2000Currentmeter)完成，寿命结果LT97(亮度衰减到初始亮度97％时达到的时间)由弗士达的FS-MP96寿命测试系统完成，所有测试均在室温大气中完成，测试结果见表1。器件的电流-亮度-电压特性由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400Sourcemeter、Keithley2000Currentmeter)测定，所有测试均在室温大气中完成，测试结果见表1。
表1、实施例8-14的器件性能总结
从表1可以看出，本发明上述的实施例8-14体现了如下技术效果：
本发明所述发光材料的分子结构为共振型大稠环体系，其中缺电子B原子和富电子的N和O原子在大稠环结构中形成共振，具有较高的荧光量子效率(>90％)，较小的单、三线态能极差，具有明显的瞬态延迟寿命以及较大的圆偏振g因子。因此，将这些材料用作掺杂有机电致发光器件发光层中的发光客体时，其最大外量子效率可高于20％，半峰宽(FWHM)在20-30nm,器件外量子效率也得到了大幅度提高。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (5)
1.一种手性热活化延迟荧光材料，其特征在于，
所述手性热活化延迟荧光材料为以下结构中的一种：
其中，虚线代表镜面。
2.一种电子器件，其特征在于，包括基质、形成在所述基质上的第一电极、第二电极、设置在所述第一电极和第二电极之间的有机层，所述有机层包含权利要求1所述的手性热活化延迟荧光材料。
3.根据权利要求2所述的电子器件，其特征在于，所述有机层包括空穴注入层、空穴传输层、电子注入层、电子传输层、空穴阻挡层、电子阻挡层中的至少一种和发光层；所述发光层包括主体材料和掺杂客体材料，所述掺杂客体材料包含权利要求1所述的手性热活化延迟荧光材料。
4.一种显示装置，其特征在于，包括权利要求2-3任一项所述的电子器件。
5.一种照明装置，其特征在于，包括权利要求2-3任一项所述的电子器件。
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Citations (2)
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| CN110872316A (zh) * | 2019-11-29 | 2020-03-10 | 清华大学 | 一种新型化合物及其应用及采用该化合物的有机电致发光器件 |
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