纯有机电致室温磷光材料与器件研究进展 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "纯有机电致室温磷光材料与器件研究进展" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Progress of Purely Organic Room-temperature Electrophosphorescent Materials and Devices" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "李", "givenname": "梦珂", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Mengke", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "李梦珂（1995-），女，河 南 商 丘 人，博士，2022 年于华南理工大学获得博士学 位，主 要 从 事 有 机 电 致 发 光 材 料 与器件的研究。Email: limk@scut.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941507&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941507&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941507&type=", "width": "24.89202881", "height": "29.88732910", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "李梦珂" }, { "name": "text", "data": "（1995-），女，河 南 商 丘 人，博士，2022 年于华南理工大学获得博士学 位，主 要 从 事 有 机 电 致 发 光 材 料 与器件的研究。Email: " }, { "name": "text", "data": "limk@scut.edu.cn" } ] ] } ], "email": "limk@scut.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "陈", "givenname": "子健", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "CHEN", "givenname": "Zijian", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "邱", "givenname": "伟栋", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "QIU", "givenname": "Weidong", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "苏", "givenname": "仕健", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "SU", "givenname": "ShiJian", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： mssjsu@scut.edu.cn", "data": [ { "name": "text", "data": "E-mail： mssjsu@scut.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "苏 仕 健（1971-），男，四 川 彭 州 人，博士，教授，博士生导师，2002 年于日本国 立 山 形 大 学 获 得 博 士 学 位，主 要 从事有机电致发光材料与器件的研究。Email: mssjsu@scut.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941520&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941520&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941520&type=", "width": "24.89202881", "height": "29.88732910", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "苏 仕 健" }, { "name": "text", "data": "（1971-），男，四 川 彭 州 人，博士，教授，博士生导师，2002 年于日本国 立 山 形 大 学 获 得 博 士 学 位，主 要 从事有机电致发光材料与器件的研究。Email: " }, { "name": "text", "data": "mssjsu@scut.edu.cn" } ] ] } ], "email": "mssjsu@scut.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "华南理工大学材料科学与工程学院 发光材料与器件国家重点实验室， 广东 广州　510641", "data": [ { "name": "text", "data": "华南理工大学材料科学与工程学院 发光材料与器件国家重点实验室， 广东 广州　510641" } ] }, { "lang": "en", "text": "State Key Laboratory of Luminescent Materials and Devices， School of Materials Science and Engineering， South China University of Technology， Guangzhou 510641， China", "data": [ { "name": "text", "data": "State Key Laboratory of Luminescent Materials and Devices， School of Materials Science and Engineering， South China University of Technology， Guangzhou 510641， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "纯有机室温磷光（RTP）材料由于能够直接利用电致激发产生的75%的三线态激子，近年来在有机电致发光领域受到研究人员的广泛关注。然而，由于纯有机材料理论上的自旋禁阻特性，使得三线态激子的辐射速率慢、激子寿命长，从而难以与非辐射耗散竞争。因此，通过有效的分子设计策略实现增强的自旋⁃轨道耦合，从而促进快速的系间窜越和磷光辐射过程，进而实现高磷光量子效率并抑制长三线态激子寿命导致的各种非辐射失活，对于开发高效的纯有机电致RTP材料与器件至关重要。本文从RTP的分子结构设计出发对近年来的纯有机电致室温磷光材料和器件进行综述，总结了含有不同重原子的纯有机磷光材料的电致发光性能，指出目前研究中需要解决的关键问题，并对其在电致发光领域的应用前景进行了展望。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Purely organic room-temperature phosphorescence （RTP） materials have received extensive attention in the field of organic electroluminescence in recent years for the direct utilization of the 75% triplet excitons generated by electro-excitation. However， due to the theoretical spin-forbidden properties of purely organic materials， triplet excitons generally possess slow radiation rates and long exciton lifetimes， making it prone to non-radiative dissipation. Therefore， achieving enhanced spin-orbit coupling through efficient molecular design strategies is essential to promote fast intersystem crossing and phosphorescence radiation processes， thereby achieving high phosphorescence quantum efficiency and suppressing non-radiative deactivation of long-lived triplet excitons. In this article， based on the structural design principles of RTP materials， we reviewed recent progresses of purely organic RTP electroluminescence materials and devices， and summarized the application of RTP materials containing different non-metallic heavy atoms in electroluminescent devices. Also， we pointed out the key problems that need to be solved in the current research， and prospected the potential application of purely organic RTP materials in the field of electroluminescence." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "纯有机室温磷光" } ], [ { "name": "text", "data": "三线态激子" } ], [ { "name": "text", "data": "电致发光" } ], [ { "name": "text", "data": "有机发光二极管" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "purely organic room-temperature phosphorescence material" } ], [ { "name": "text", "data": "triplet exciton" } ], [ { "name": "text", "data": "electroluminescence" } ], [ { "name": "text", "data": "organic light-emitting diode" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "能够有效利用长寿命三线态激子的纯有机磷光材料在有机发光二极管（OLED）、自旋电子学、生物成像等领域都已经得到了广泛的研究。其中，有机发光二极管作为新一代发光显示器件，具有全固态、自发光、广视角、快响应、轻薄柔性等优点，备受学术界和产业界关注。按照自旋统计学规律，电致情况下电荷注入后复合将产生25%的单线态激子和75%的三线态激子。因此，开发能够有效利用三线态激子的高性能有机发光材料，以实现100%的电致激发态的利用一直是OLED领域的关键科学问题。1998年，基于重金属锇和铂的磷光配合物利用增强的自旋-轨道耦合（SOC）作用实现了磷光主导的OLED器件，为有机电致发光中三线态激子的直接利用提供了思路" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } } ], "rid": [ "R1", "R2" ], "text": "1-2", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "纯有机材料由于单线态和三线态之间理论上的自旋禁阻特性，使得三线态激子的辐射速率慢、激子寿命长，容易通过分子运动产生非辐射耗散，或被多种猝灭因子（水、氧等）猝灭。通常，强的分子间相互作用通过限制分子内和分子间运动，有利于稳定长寿命的三线态激子，从而实现有效的磷光发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } } ], "rid": [ "R3", "R4" ], "text": "3-4", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。目前，利用具有强相互作用的刚性环境抑制非辐射失活是实现高效纯有机RTP体系的研究热点和主要途径。近年来，已开发的高效纯有机RTP 材料体系主要包括小分子晶体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } } ], "rid": [ "R5", "R6", "R7" ], "text": "5-7", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、主客体共晶" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R8", "R9" ], "text": "8-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、大环超分子框架" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、聚合物薄膜" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } } ], "rid": [ "R11", "R12" ], "text": "11-12", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等，多应用于安全防伪及生物成像等领域。研究人员对于纯有机RTP 材料的相关研究集中于晶体及刚性主客体体系，依赖于高度有序的晶体结构及强烈的分子间相互作用对非辐射失活的抑制" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } } ], "rid": [ "R13", "R14", "R15", "R16" ], "text": "13-16", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，已有的纯有机RTP材料的研究中，能够有效应用在电致发光领域的相对较少。尽管如此，由于无重金属元素依赖的纯有机室温磷光材料具有低成本、低毒性、分子设计多样性以及潜在的高效率等特性，在有机电致发光领域表现出较大的应用潜力。目前，学术界已有一些基于纯有机RTP材料的电致发光器件的初步探索，并取得了一定的成果。本综述从分子结构设计的角度讨论应用于电致发光器件的纯有机室温磷光材料，总结其电致发光性能及研究进展，并对其应用前景进行展望。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　纯有机室温磷光材料的光物理过程" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "源于三线态的纯有机室温磷光的产生主要涉及两个关键性的光物理过程：系间窜越（ISC）和磷光辐射过程。决定有机材料中磷光性能的两个关键参数是磷光量子效率（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941528&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941523&type=", "width": "3.64066648", "height": "4.48733330", "fontsize": "" } } } ] }, { "name": "text", "data": "）和磷光寿命（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941538&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941534&type=", "width": "3.04800010", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）。" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941558&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941542&type=", "width": "3.64066648", "height": "4.48733330", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941567&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941563&type=", "width": "3.04800010", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "取决于单线态激子向三线态激子的系间窜越效率" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941575&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941570&type=", "width": "5.41866684", "height": "4.48733330", "fontsize": "" } } } ] }, { "name": "text", "data": "、磷光辐射速率" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941584&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941580&type=", "width": "2.96333337", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "、以及磷光非辐射速率" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941596&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941589&type=", "width": "3.47133350", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "，具体可以表示为：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（1）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941604&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941600&type=", "width": "20.15066719", "height": "4.48733330", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF1" } }, { "name": "dispformula", 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"）。对于电致发光而言，电子和空穴重组直接产生75%的三线态激子，因此，对三线态激子辐射跃迁的有效利用是实现高效电致磷光的关键。而纯有机材料的磷光辐射发生在自旋多重度不相同的电子态间，使得三线态激子具有长寿命的特征，在构筑器件所需的无定形薄膜状态下极易发生非辐射失活。因此，尽可能地实现增强的自旋-轨道耦合，从而实现快速的系间窜越和磷光辐射，抑制三线态激子的多种非辐射失活过程，是实现高效RTP的关键" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } } ], "rid": [ "R17", "R18" ], "text": "17-18", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。目前，研究人员已采取了一系列有效的分子设计策略来实现增强的SOC效应" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } } ], "rid": [ "R19", "R20", "R21" ], "text": "19-21", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。根据不同多重度的电子态间的自旋-轨道耦合矩阵元，如单线态（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941633&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941629&type=", "width": "3.04800010", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）-三线态（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941640&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941636&type=", "width": "3.72533321", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）间的自旋-轨道耦合矩阵元" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941648&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941644&type=", "width": "25.73866653", "height": "5.16466665", "fontsize": "" } } } ] }, { "name": "text", "data": "（其中，" }, { "name": "italic", "data": [ { "name": "text", "data": "Z" } ] }, { "name": "text", "data": "为原子序数），利用重原子效应实现增强的自旋-轨道耦合作用，进而促进单线态激发态到三线态激发态的系间窜越以及三线态激发态到基态的辐射跃迁过程，是实现高磷光量子效率，进一步实现其在高效电致发光器件上应用的有效途径。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　硫族元素在纯有机电致室温磷光材料中的应用" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "目前，基于纯有机室温磷光材料的电致发光器件的应用探索中，研究较多且性能最好的是含有ⅥA族非金属元素硫、硒的结构。相对于传统纯有机电致发光材料中的碳、氢、氧、氮等元素，硫族元素具有较大的相对原子质量，利用其重原子效应能够有效地促进单三线态之间的SOC；同时，其外围孤对电子轨道可以在跃迁过程中引入不同的轨道成分，根据EL-Sayed规则，可以有效促进具有不同多重度的电子态间的自旋翻转" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } } ], "rid": [ "R22", "R23" ], "text": "22-23", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与重原子卤素相比，硫族元素能够通过引入芳香杂环来更好地参与共轭，从而更加有效地促进系间窜越和磷光辐射过程，实现高的电致发光性能。近年来，有一些含硫、硒的芳香杂环材料已经被成功应用于纯有机电致磷光二极管中。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　含硫原子的纯有机电致室温磷光材料" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "硫原子具有[Ne]3s" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "3p" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的外围电子排布，同时，成键后有两对孤对电子，可以有效提高分子激发态的n-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "跃迁成分，满足EL-Sayed规则实现自旋翻转。另一方面，硫原子较大的原子半径使得含硫杂环一般具有较为扭转的结构，对于通过自旋-振动耦合增强SOC有重要的促进作用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } } ], "rid": [ "R24", "R25", "R26" ], "text": "24-26", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2013年，Lupton等通过引入酚嗪-噻吩基团增强分子的自旋-轨道耦合，首次在室温下观测到长寿命的纯有机电致磷光发光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。虽然器件效率非常低且电致光谱中的磷光成分较少，但是该工作为低成本磷光OLED器件提供了新的可能性。随后，Lupton等继续研究了噻吩连接位点的同分异构效应对磷光发光性能的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。电子自旋共振和理论计算表明，噻吩基团的不同共轭会影响自旋密度分布以及高能n-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "态的耦合，从而影响三线态激子的辐射以及非辐射跃迁。该类结构mT-3DTPZ、 hexT-5DTPZ、 hexT-3DTPZ（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "）等由于较低的器件性能，作者仅对其电致发光光谱进行了表征，证实了存在三线态的直接辐射跃迁。2013年，Ceroni等报道了含多个硫原子的苯硫醚化合物hex-mPTPh（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "），在固态下，由于分子间的C—H⋯π相互作用，硫醚键运动被抑制，粉末呈现出非常高的磷光量子效率80%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，将该材料作为发光客体制备的溶液加工电致发光器件，由于在无定形薄膜中非常低的发光量子产率，磷光器件效率仅为0.1%（0.5 cd/A）。利用分子构象对于激发态性质的重要影响，Bryce等通过甲基位阻单元调控吩噻嗪-二苯甲酮的扭转角来调控光物理特性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，平面的电荷转移分子OPM表现出RTP主导的发光，而扭转电荷转移分子OMP显示热活化延迟荧光（TADF）性质的发射（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "）。相比于TADF的电致发光器件，基于OPM的磷光OLED器件效率较低，最大外量子效率仅0.6%。通过将咔唑单元和硫族元素（Q、S、Se）与中心苯核相连接，Wang等开发了基于星形结构的有机磷光材料，在掺杂膜和纯膜状态下均表现出长寿命的磷光发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，引入硫原子的材料CzS（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "）在纯膜中实现了相对最高的磷光量子效率5.0%及最长的寿命356 ms。基于CzS的溶液加工OLED器件，通过调节荧光和磷光的双发射，实现了单分子白光，CIE坐标（0.36，0.38），器件最大外量子效率为0.12%。因此，虽然含硫原子的材料可以实现在固态下较高的光致发光量子产率（PLQY），但是，在无定形薄膜状态下，由于强非辐射跃迁，实现高磷光量子产率仍然是实现高效电致磷光器件的主要障碍。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "应用于电致发光器件的含硫杂环纯有机室温磷光分子结构" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Purely organic RTP molecular structures containing sulfur heterocycles for electroluminescent devices" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941652&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941658&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941655&type=", "width": "159.50701904", "height": "88.87817383", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2019年，Wang等开发了基于吩噻嗪-萘基的化合物DPTZN（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "），其在晶体中显示出室温磷光发射特性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。当和N型三嗪-咪唑化合物TRZ-BIM共混时，磷光效率相比于单组分体系有显著提高，量子效率达到了38%，基于10% DPTZN∶TRZ-BIM共混薄膜的OLED器件最大外量子效率达到11.5%。然而，其共混促进磷光的原因仍需进一步探索。除了利用硫的重原子效应外，为进一步增强自旋-轨道耦合，最近，Su等设计了一种具有“柔性”和扭曲结构的噻蒽-嘧啶基有机化合物mTEPm（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "），其柔性的分子骨架具有较强的激发态构象弛豫和分子振动，对自旋-振动耦合具有重要的促进作用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在无定形非掺杂薄膜下，该化合物表现出快速的系间窜越过程和较高的磷光辐射跃迁速率（1.1×10" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "），最终实现了非掺杂的纯有机磷光电致发光器件，且最大外量子效率可以达到7.98%，是目前基于非掺杂纯有机电致磷光器件的最高性能。不同于一般TADF或者RTP的扭转给-受体结构的分子设计，Su等进一步通过将多个硫原子引入异构化的多环芳烃并五苯和戊芬中，开发了一组新型高效的硫杂环稠环化合物bTEoCN、bTENCO和bTEpCN（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "），并提出了一种高效率且发光机理可调控的热活化延迟荧光和室温磷光OLED的分子设计概念" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，bTEoCN实现了室温磷光主导的光致和电致发光，相应器件的EQE可以达到8.7%，证明了含硫杂环材料体系在构筑高效OLED器件中的潜力。同时，其在实现纯有机电致磷光器件方面也展示出较大的优势。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　含硒原子的纯有机电致室温磷光材料" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "相对于硫原子而言，硒原子具有更高阶的外围电子轨道（[Ar]3d" }, { "name": "sup", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "4s" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "4p" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "），在跃迁过程中能够利用外围轨道的参与更有效地促进自旋翻转。目前，基于含硒杂环的电致RTP材料的研究取得了较大的进展。其中，吩硒嗪是一种具有室温磷光特性的含硒的氮杂环单元，其衍生物的电致发光性能受到广泛关注。2019年，Lee等首次报道了含有吩硒嗪单元的电致发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。以吩硒嗪作为给体、三苯基三嗪作为受体的材料PSeZTRZ（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）在光致发光条件下表现出同时具有TADF和RTP发光性质的双构象发光，然而在OLED器件中其电致发光主要表现为TADF机理。2020年，他们进一步通过引入两个吩硒嗪单元，获得了一系列含硒的有机电致发光材料PSe1、PSe2和PSe3（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "），并实现了磷光主导的电致发光器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。不仅通过吩硒嗪单元中硒原子的引入提供重原子效应，同时激发态下硒原子的p" }, { "name": "sub", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "轨道到苯环π轨道的跃迁也可以产生轨道角动量的变化从而协同促进自旋-轨道耦合。因此，这些材料在非晶态的掺杂薄膜下均表现出磷光发射，磷光量子效率高达35%，磷光寿命为700 μs。以PSe1作为发光客体的掺杂OLED器件表现出10.7%的最大外量子效率，这是首次报道器件外量子效率超过10%的纯有机电致室温磷光材料。之后，Lee等还研究了苯基吩硒嗪PhSe上的不同取代基（苯基、甲基、叔丁基）对磷光性能的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "37", "type": "bibr", "rid": "R37", "data": [ { "name": "text", "data": "37" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，甲基以及叔丁基取代的mPhSe和BuPhSe（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）由于烷基链的空间位阻能够有效抑制三线态激子的聚集猝灭效应（ACQ），从而实现了33.9%和34.0%的PLQY。在OLED器件中，BuPhSe实现了9%的最大外量子效率，同时由于抑制的ACQ，在较高掺杂浓度下仍有相对好的效率滚降。在此基础上，Lee等基于mPhSe进行修饰，在吩硒嗪上进一步引入了9位取代的苯基咔唑作为第二发色团合成了PSe3Cz分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。该化合物中，吩硒嗪单元可以有效地促进自旋-轨道耦合；同时，第二发色团苯基咔唑的引入能够进一步提升发光效率，从而在薄膜状态下实现了50.2%的高PLQY，磷光寿命为820 μs。相应的电致磷光OLED器件在540 nm处实现了13.2%的最大外量子效率。除了作为发光客体，Lee等在吩硒嗪单元上引入咔唑基团获得了PSeZ9Cz（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究表明，PSeZ9Cz能够实现较高的激子利用率，将其作为发光客体制备的室温磷光OLED器件实现了11.4%的最大外量子效率。进一步将其作为敏化剂，他们研究了通过室温磷光材料敏化传统荧光材料的电致发光器件。通过室温磷光敏化剂来有效利用三线态激子并通过能量转移到传统荧光客体中实现高效荧光。他们在掺杂10%的室温磷光敏化剂PSZ9Cz和0.8%的传统荧光客体TBRb的敏化器件中，成功实现了最大外量子效率8.1%的高效传统荧光OLED器件。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "应用于电致发光器件的含硒杂环的纯有机室温磷光分子结构" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "Purely organic RTP molecular structures containing selenium heterocycles for electroluminescent devices" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941663&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941671&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941667&type=", "width": "156.23217773", "height": "130.91943359", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "除了只含有给体单元的分子设计策略以外，基于吩硒嗪衍生物的给-受体（D-A）型纯有机磷光分子结构也有报道。2020年，Lee等通过引入含有n电子的苯甲酰基受体合成了PSeBZ（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，这种D-A型分子设计策略也促进了反向系间窜越（RISC）过程，导致TADF和RTP双发射。在掺杂OLED器件中，PSeBZ实现了5.7%的最大外量子效率，在较低的驱动电压下，560 nm的磷光发射是电致发光的主要成分；随着驱动电压的升高，较高的电流密度导致严重的三线态激子-三线态激子湮灭（TTA），电致发光光谱向TADF成分蓝移，存在光谱不稳定问题。此外，利用TADF材料双[4-(9,9-二甲基-9,10-二氢吖啶)苯基]硫砜（DMAC-DPS）作为敏化剂，他们还研究了双苯甲酰基取代的吩硒嗪衍生物PSeBBZ（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究发现，引入具有高三线态的TADF材料DMAC-DPS作为敏化剂，利用从DMAC-DPS到PSeBBZ的能量转移过程能够有效增加激子利用率并且抑制三线态激子猝灭，从而实现高磷光效率。通过TADF敏化剂的加入，基于PSeBBZ的OLED器件的最大外量子效率从4.1%提高到7.2%，最大发光亮度从236.7 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "增加到了967.3 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "。除了苯甲酰基受体，Takeda等也通过将吩硒嗪给体与吩嗪受体相结合，研究了具有D-A-D型结构的化合物PSeZ-DBPHZ-PSeZ的光电性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同样地，由于扭转结构带来的RISC过程增加，其光致和电致发光光谱均表现出荧光磷光双发射，相应器件的最大外量子效率为4.35%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "除了目前研究较多的吩硒嗪衍生物以外，其他含有硒原子的结构单元也被用于构筑电致磷光材料。例如，Huang等通过引入硒吩单元与羰基受体连接，合成了D-A型发光材料PhCz-Se（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "43", "type": "bibr", "rid": "R43", "data": [ { "name": "text", "data": "43" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在晶体条件下，表现出438 nm的荧光和590 nm的磷光双发射。基于荧光磷光双发射的光物理特性，其相应的OLED器件在4 V的驱动电压下得到了CIE色坐标为（0.30，0.29）的冷白光发射，器件的最大外量子效率为1.56%。但是，同样由于长的磷光寿命113.1 μs，器件在高电压下存在严重的TTA，导致明显的光谱不稳定问题。Wang等以硒杂蒽酮为电子受体单元，与咔唑电子给体单元结合，利用硒原子的重原子效应与含n轨道羰基的协同作用，构建了D-A型RTP分子CzSe（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在1%的聚甲基丙烯酸甲酯（PMMA）的掺杂薄膜中，该化合物表现出峰值为462 nm的室温磷光发射，PLQY为31.2%，磷光寿命为360.1 μs。由于咔唑与硒杂蒽酮间相对小的扭转角，CzSe分子具有较大的单三线态能级差，且三线态表现为局域态的发光。在以3,3-二(咔唑基)联苯（mCBP）作为主体的掺杂器件中，CzSe实现了最大外量子效率为8.9%的蓝光电致磷光。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　含有其他杂原子的纯有机电致室温磷光材料" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "尽管目前研究较多且性能较好的电致室温磷光材料是基于含硫、硒原子的结构，除此之外，也有一些基于其他杂原子的有机电致磷光材料的研究和应用探索（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "）。卤族元素由于相对大的原子质量，也被用于构建有效的纯有机磷光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2016年，Anzenbacher等开发了基于溶液加工的有机电致磷光材料A1（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "），通过引入重原子溴和磷，该化合物的电致发光光谱显示明显的磷光主导的发射，然而器件的效率较低，最大外量子效率仅为0.25%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。He等将溴原子引入聚苯乙烯类结构中，同样开发了基于溶液加工的电致磷光材料Br-PPV-CHO（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。该化合物在PVK掺杂薄膜中的PLQY为12.2%，然而当将其用于电致发光器件时，器件效率仍然较低，最大亮度仅194 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "。同样利用溴的重原子效应，2019年，Lee等利用溴原子修饰的27PNDO作为发光客体，同时利用溴原子修饰的化合物27QNX（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "）作为辅助主体，1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯（TPBi）作为常用主体，所制备的OLED器件实现了磷光主导的发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究发现，当将27PNDO掺杂进单独的TPBi主体中时，没有检测到磷光发射，主要是由于TPBi无法提供一个刚性的环境，使客体分子易非辐射失活。而理论计算表明，辅助主体27QNX除了提供外部重原子效应外，还能与客体分子形成紧密的π-π堆积，进而抑制三线态激子的非辐射损失，实现有效的磷光发射。同时，由于27PNDO和27QNX较强的平面性，其双组分薄膜极易结晶，因此需要掺杂在常用主体TPBi中抑制结晶，提高成膜性。然而，由于该三元发光层较差的空穴注入和传输特性，器件的最大外量子效率仅为0.11%。2020年，Kim等通过将三氟甲基和溴原子引入二苯基芴，利用增强的SOC效应和抑制的非辐射失活，开发了纯有机磷光材料BrPFL-TFK（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。将其掺杂在无定形态的聚合物主体中时，可以实现24%的磷光量子效率。同时，作者探究了将其掺杂在不同主体材料中的磷光性能，当掺杂在1,3-二(咔唑-9-基)苯（mCP）和3,3'-二(9H-咔唑-9-基)-1,1'-联苯（CBP）中时，由于激基复合物的形成，无法实现单一的磷光发射；当使用PPT作为主体材料时，由于其较深的HOMO能级和较浅的LUMO能级，无法与客体分子形成激基复合物，从而其相应的电致发光器件实现了单一的磷光发射，且实现了2.5%的最大外量子效率。然而，由于其毫秒级的长三线态激子寿命，该器件面临严重的效率滚降。由此可见，虽然溴重原子的引入有利于通过强的自旋-轨道耦合促进有机材料中三线态激子的直接辐射跃迁，然而溴原子的引入一般也会导致材料的稳定性较差且光致发光量子效率降低。因此，含溴原子的纯有机材料在电致发光器件上的应用效果并不理想，器件效率远低于含硫、硒原子的纯有机材料。此外，目前也有一些利用磷原子的重原子效应增强RTP性能的报道，大多集中于晶体和主客体体系中。由于磷原子的稳定性较差，其在电致发光器件中的应用报道相对较少。其中，2020年，Zhu等报道了基于手性分子的纯有机电致室温磷光材料BINAP（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "），磷原子上的孤对电子和大的原子序数使得BINAP同时具有蓝绿光的荧光发射和深红光的磷光发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同时作者研究发现，外消旋的BINAP具有比左旋和右旋BINAP更好的磷光性能，主要是由于外消旋的BINAP晶体中，R-BINAP和S-BINAP交叉排列，显著降低了双分子的猝灭通道（TTA等），从而实现了对非辐射失活的抑制。基于外消旋的BINAP，其电致发光器件实现了比光致发光下更平衡的荧光和磷光强度，从而实现了单分子白光发射，器件最大外量子效率1.6%。该工作也证明了纯有机磷光材料在实现单分子白光方面具有一定的潜力。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "应用于电致发光器件的含溴、磷、氮、氧等杂原子的纯有机室温磷光材料。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "Purely organic RTP molecular structures containing bromine， phosphorus， nitrogen and oxygen heteroatoms for electroluminescent devices." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941675&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941685&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941679&type=", "width": "156.79724121", "height": "110.58239746", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "此外，根据EL-Sayed规则，具有不同跃迁成分的轨道之间更容易发生电子自旋的翻转，通过引入具有n-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "跃迁特性的氮、氧等杂原子的RTP材料也有相关报道。2019年，Zhang等通过在双咔唑化合物上引入二苯甲酮和二苯基砜类取代基，设计了一系列具有聚集诱导磷光特性的化合物BCZ1-4（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "），该系列材料显示出双磷光发射的特性，在固态下的磷光量子效率高达64%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。利用其聚集诱导发光特性，将该系列材料作为单发光层制备的非掺杂OLED器件实现了相对较小的效率滚降。其中，基于BCZ1化合物的OLED器件实现了5.8%的最大外量子效率，超过了纯荧光OLED器件的理论极限（" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "）。而重原子溴修饰的化合物BCZ3由于较低的发光效率，并未探索其电致发光性能。2021年，An等利用双发射特性基于二苯甲酮受体报道了一种具有TADF和RTP特性的D-π-A-π-D型化合物NP2BP（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "），该化合物在PMMA掺杂薄膜中表现出TADF特性，在固态中呈现蓝光TADF和橙光RTP双发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。相应地，以NP2BP作为单发光层的非掺杂OLED器件呈现出近白光发射，CIE坐标为（0.23,0.32），最大外量子效率为1.09%。2021年，Wang等基于氧原子桥接的D-O-A结构，开发了一种高效RTP聚合物P(DMPAc-OTPTrz)（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与传统的D-A结构相比，在给体和受体之间插入氧原子一方面可以减少空穴-电子轨道重叠以抑制电荷转移荧光，另一方面还可以增强SOC效应以促进ISC和磷光辐射通道。因此，在光致激发下可以观察到明显的RTP发射。基于该D-O-A结构的聚合物发光二极管（PLEDs）显示磷光主导的电致发光，且实现了高达9.7%的外量子效率，为基于纯有机RTP聚合物的PLEDs的发展提供了重要参考。" } ] }, { "name": "table", "data": { "id": "T1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "典型纯有机室温磷光材料在薄膜状态下的光物理性质参数及器件性能（EQE > 5%）" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab.1" } ], "title": [ { "name": "text", "data": "Photophysical properties in film state and device performance of typical purely organic RTP materials （EQE>5%）" } ] } ], "note": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "* 纯有机室温磷光材料在薄膜状态下，（a）磷光发光峰位置，（b）光致发光量子效率，（c）对应磷光发光峰处的寿命，（d）相应器件的最大外量子效率。" } ] } ] } ], "table": [ { "head": [ [ { "align": "center", "style": 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"目前国内外针对基于纯有机室温磷光材料的电致发光器件已取得了初步的研究成果，揭示了基于纯有机RTP材料的开发有可能实现高效的电致发光器件。然而，随着研究的不断深入，目前的这些探索在展示了纯有机RTP材料作为低成本、高效率OLED 发光材料的潜力的同时，也揭示了其仍然面临着各种技术问题和挑战，仍需要在这些方面进行进一步的研究探索以实现可在显示和照明领域商业化应用的 OLED。主要包括以下关键挑战：一方面，目前大多数高效的纯有机磷光材料体系均需借助于晶体密堆积等刚性的环境，其在无定形薄膜状态下面临严重的非辐射损失，导致薄膜中的磷光量子效率较低。尽管一些材料尝试了在有机电致发光上的应用，然而器件效率有待进一步提升，且真正参与辐射跃迁的磷光成分仍然较少。另一方面，器件的稳定性问题也有待解决，伴随着有机材料中三线态激子的长寿命特征，器件性能也表现出一些明显的缺陷，主要包括由于长寿命三线态激子的猝灭而导致的效率随电流大幅度下降，以及高电流密度下三线态激子的发光成分猝灭而导致的电致发光光谱不稳定等。因此，在构筑器件所需的无定形薄膜状态下实现高效的纯有机磷光发射仍然十分困难，如何实现该类体系中的三线态激子在OLED中的高效利用仍是一个亟待解决的难题，需要进一步从材料设计、器件结构等方面进行优化。从材料设计方面，引入具有强自旋-轨道耦合效应的结构单元，提高系间窜越效率以增加三线态激子成分；同时缩短三线态激子的寿命，避免发生严重的三线态激子猝灭及多种非辐射失活，实现高磷光量子效率；从目前发展的有机磷光体系来看，硫族元素的引入在实现高效磷光OLED方面显示出较大的优势和应用前景。从器件结构方面，选择能级匹配的界面功能层，深入认识主体材料与磷光客体的相互作用机理，开发能够实现高三线态激子利用率的高性能器件结构。通过进一步的高效有机磷光材料的开发以及高性能器件结构的优化，有望基于纯有机室温磷光材料发展实用化的低成本、高效率电致发光器件。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": 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