紫外/深蓝OLED发光材料研究进展 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "紫外/深蓝OLED发光材料研究进展" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Progress of Ultraviolet/Deep-blue OLED Luminescent Materials" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "娄", "givenname": "敬丽", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LOU", "givenname": "Jingli", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "娄敬丽（1999-），女，山东聊城人，博士研究生，2017年于青岛科技大学获得学士学位，主要从事有机电致发光二极管的研究。Email: superwomanljl@163. com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941888&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941895&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941890&type=", "width": "24.89199829", "height": "29.88732910", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "娄敬丽" }, { "name": "text", "data": "（1999-），女，山东聊城人，博士研究生，2017年于青岛科技大学获得学士学位，主要从事有机电致发光二极管的研究。Email: " }, { "name": "text", "data": "superwomanljl@163. com" } ] ] } ], "email": "superwomanljl@163. com", "deceased": false }, { "name": [ { "lang": "zh", "surname": "黎", "givenname": "刚刚", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Ganggang", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "王", "givenname": "志明", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Zhiming", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "corresp", "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： wangzhiming@scut.edu.cn", "data": [ { "name": "text", "data": "E-mail： wangzhiming@scut.edu.cn" } ] }, { "rid": "cor2", "lang": "en", "text": "wangzhiming@scut.edu.cn", "data": [ { "name": "text", "data": "wangzhiming@scut.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "王志明（1983-），男，吉林松原人，博士，研究员，博士生导师，2011年于吉林大学获得博士学位，主要从事芳基杂环高效率深蓝光材料的设计及新型AIE荧光探针的研究。" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941898&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941904&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941901&type=", "width": "24.89199829", "height": "29.88732910", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "王志明" }, { "name": "text", "data": "（1983-），男，吉林松原人，博士，研究员，博士生导师，2011年于吉林大学获得博士学位，主要从事芳基杂环高效率深蓝光材料的设计及新型AIE荧光探针的研究。" } ] ] } ], "email": "wangzhiming@scut.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "唐", "givenname": "本忠", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "TANG", "givenname": "Benzhong", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "华南理工大学 材料科学与工程学院， 广东 广州　510640", "data": [ { "name": "text", "data": "华南理工大学 材料科学与工程学院， 广东 广州　510640" } ] }, { "lang": "en", "text": "School of Materials Science & Engineering， South China University of Technology， Guangzhou 510640， China", "data": [ { "name": "text", "data": "School of Materials Science & Engineering， South China University of Technology， Guangzhou 510640， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "有机电致发光材料和器件（OLED）经过三十余年的发展已经基本完成了从基础科学研究到产业化商品的蜕变过程，而由于蓝紫发光材料的分子禁带（" }, { "name": "text", "data": ">" }, { "name": "text", "data": "3.0 eV）与器件运行中载流子注入/传输平衡之间的固有矛盾，加之人眼在蓝光区域的敏感度降低等问题，蓝光器件的整体性能远远落后于其他光色。因此，综合性能优异的紫外/深蓝光材料和相关分子设计理论已成为实现OLED独领“新一代显示照明技术”的关键突破点。本文主要介绍了近十年来紫外/深蓝OLED发光材料（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "<" }, { "name": "text", "data": "430 nm）的研究进展，并从材料结构与机制等方面进行了归纳，旨在推动更多宽禁带发光材料的设计和相关理论的完善和发展。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "After more than 30 years of development， organic electroluminescent materials and organic light-emitting diodes （OLEDs） have almost completed the transformation process from basic scientific research to commercialization products. However， due to the inherent contradiction between the wide band-gap （exceed 3.0 eV） of ultraviolet and deep-blue luminescent materials and the carrier-injection ability and transport balance during device operation， with the decreasing sensitivity of human eyes in blue light area， the overall performance of ultraviolet and deep-blue light-emitting devices lag far behind other colors light-emitting devices. Therefore， the ultraviolet and deep-blue materials with excellent comprehensive performance and related molecular design theories have become the key breakthrough points for OLED to take the only place to lead the “New generation of display and lighting technology”. In this review， the ultraviolet and deep-blue luminescent materials （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": " below 430 nm） which were applied for organic light-emitting diodes in recent ten years are introduced briefly and summarized from the points of material structure and luminescence mechanism， hoping to promote the development of more and more excellent electroluminescent materials with wide band-gap and the improvement of the relevant theories." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "OLED" } ], [ { "name": "text", "data": "紫外光" } ], [ { "name": "text", "data": "深蓝光" } ], [ { "name": "text", "data": "分子设计理论" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "organic light-emitting diodes" } ], [ { "name": "text", "data": "ultraviolet" } ], [ { "name": "text", "data": "deep-bule" } ], [ { "name": "text", "data": "molecular design theory" } ] ] } ], "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": "有机电致发光二极管（Organic light-emitting diodes，OLED）是指通过发光介质将电能转化为光能的新一代发光器件，发光层以有机材料为主。在外加电场的作用下，电子和空穴分别由金属阴极和ITO阳极相向注入，穿过势垒向发光层移动，在发光层复合形成激子，激子跃迁辐射光子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。有机电致发光二极管具有柔性、低能耗、高分辨率等独特优势，在固态照明和平面显示等领域" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } } ], "rid": [ "R2", "R3" ], "text": "2-3", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "已经实现了大规模商业化应用。其中，高效、色度稳定、长寿命的红光、绿光、天蓝光的有机发光材料如雨后春笋般层出不穷，为商用的单色光和白光OLED提供了更加丰富的选择" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；光谱上200~400 nm波段为紫外光，紫外光在医学、环境、防伪等领域有着广泛的应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，深蓝光是实现高效节能OLED的关键要素。但是，高品质且综合性能优异的蓝光、深蓝光及紫外光材料相对匮乏，其对应的材料设计理论也相对缺失，因而已成为实现OLED独领“新一代显示照明技术”的关键突破点。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "根据目前的器件设计工艺和结构，提高紫外/深蓝光材料的综合品质对于实现高效、节能的OLED至关重要。一方面，具有宽带隙、高效率和高激子利用率的蓝紫光有机发光材料可以直接作为发光层，制备高性能的单色光OLED来提高显示和照明的色彩饱和度和色彩还原度" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；另一方面，蓝紫光材料具有高三线态能级的潜在属性，可以用做传统荧光、磷光或白光OLED的掺杂或敏化主体材料，借助主-客体间的能量转移等机制，综合利用其高激子利用率和客体材料高光致发光量子产率特点，以实现兼具高效、高亮度、高激子利用率的电致发光器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R7", "R8", "R9" ], "text": "7-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在器件优化使用材料的过程中，真正满足商用的、综合电致发光性能优异的短波长有机发光材料相对匮乏，一方面源于可兼具高效宽禁带发光和电荷注入/传输平衡的结构基元相对较少，另一方面则是材料设计理论与电致发光机制间未能建立有效的指导策略。因此，本文总结了近十年来各国科学工作者在蓝紫OLED发光材料制备领域的研究成果，归纳了电致发光主峰位在430 nm以下的有机发光材料，并对比其结构和性能提出一些有待进一步验证和讨论的策略及建议，旨在从材料的角度为后续高效、稳定的紫外/深蓝发光器件的发展提供积累，推动宽禁带发光材料的设计和相关理论的完善和发展。其中，部分观点系笔者多年研究经验的认知与总结，不当之处请大家酌情采纳。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　关键科学问题" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "事实上，要实现高效的蓝紫光发射，必须明确电致发光和光致发光的机制的差异，才会更加深刻地理解OLED发光材料设计的基本原则和潜在矛盾的调节策略。通常，光致发光过程是处于基态的分子通过吸收对应的光子能量而变成激发态，而根据跃迁准则，获得的激子则一定为单线态激子；部分单线态激子可以通过系间窜跃（Intersystem crossing，ISC）过程变为三线态激子而展现出更加丰富的用途，例如分子光物理性能分析" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R10", "R11" ], "text": "10-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "和光动力治疗" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等。换句话说，光致发光过程中的三线态激子一定来源于单线态的转化，不同材料的转化速率存在差异。因此，光致发光效率代表分子对于激发态能量的分配能力，效率越高，分子用于辐射跃迁的比例越大。但是，对于电致发光过程，激子生成来源于电极两侧的载流子注入和复合。在暂时不考虑器件中用于辅助注入和传输的功能层的性能因素的前提下，单线态和三线态的生成具有相同的截面；但综合考虑各方面的因素后，普遍认可的比例为1∶3，如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（a）所示。因此，对于最为常见的电致荧光器件来讲，要获得更高的激子利用效率，高效的反系间窜跃（Reverse intersystem crossing，RISC）过程就成为了提高效率的关键" }, { "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": "。所以，目前界定材料更新世代的重要标志也是以激子反系间窜跃的形式差异来划分的。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "（a）光致发光与电致发光；（b）ICT效应在D-A构型与非D-A构型中的不同表现；（c）有机电致发光二极管的常见结构。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 1" } ], "title": [ { "name": "text", "data": "（a）Photoluminescence and Electroluminescence.（b）The different performances of intermolecular charge transfer effect in D-A configuration and non-D-A configuration.（c）The common devices structure of organic light-emitting diodes." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941907&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941913&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941910&type=", "width": "150.52239990", "height": "89.30459595", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "基于上述分析，电致发光相比于光致发光要更多地考虑激子生成的因素。从积极方面来讲，强化载流子注入方式可以更有效地提高器件的电致发光性能，从而导致光致发光效率较低的材料也有希望制备出高性能器件；而从相对难度来讲，高效电致发光材料的获得需要考虑更多的载流子注入和迁移的因素。而当分子禁带增加或降低到一定程度时，考虑这些因素难度则会进一步加大。因此，深蓝光和深红光材料优选仍是目前较为活跃的课题。虽然重金属效应的引入能够提高激子的利用率，但会导致发光材料的禁带在蓝光领域难有显著的突破，因此，纯有机发光材料成为大家更加关注的焦点。要在材料设计上有所突破，不能回避需平衡以下几个问题。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第一，光色纯度与有效共轭长度：通常情况下，发光分子体积与有效共轭并不是等同的概念，二者可以借助分子设计、理论计算和构效关系总结实现一定程度的平衡。考虑分子体积的主要因素除了发光效率、载流子跳跃式传输、堆积形式等稳定性外，更主要的是分子体积是保证电致发光氧化还原过程中自由基阴阳离子的化学稳定性、防止分子偶联、不可逆氧化还原等的关键" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（b）所示，对于蓝紫光的光色控制，常采用增加D-A结构的扭转角等方式来限制真正参与跃迁的电子数目及范围，从而实现对共轭长度的控制，达到“大体积短共轭”的目的，以获得热学稳定性更高、光色更蓝、载流子相对平衡的体系；但是，通常这种策略会导致材料的光色越蓝，相对的光致荧光量子产率越低，这主要是由于光生激子过程中参与的电子数目有限，而且分配过程中受到的干扰因素（杂质、构象差异等）相对较多，从而使得光学测试的结果达不到理想的目标。从激子生成机制的角度讲，这类材料的电致发光性能不一定太差，特别是其作为母体等材料使用时，往往会有出其不意的效果。所以很多蓝紫光材料在非掺器件中的性能表现平平，却在掺杂器件应用中值得期待。但从激子分配的角度讲，如果想获得更好的非掺杂蓝紫光材料，必须要解决光致发光过程中非辐射跃迁比例过大的问题，否则器件效率很难在方法论上有本质的提高，都是在“随机”讨论。例如，目前兴起的“多重共振”理论从某种程度上成为解决上述问题的一个例证" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，但是如何解决光色蓝移至400 nm附近仍是不小的科学问题，尽管其在照明显示应用上的意义没有那么大。综上，分子体积和光色的平衡是蓝紫光材料设计中一个不可绕过的问题，也是分子设计理论和材料体系突破的关键。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第二，宽禁带与载流子注入/传输：由于电致发光过程中的激子生成一定要依赖于载流子的复合，所以有效的载流子注入和传输则是保证激子生成的关键" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，工业上严格筛选空穴和电子的注入层和传输层材料，以保证更多的载流子进入发光层，从而实现最大限度地发挥发光层的效能。通常判断载流子注入情况以分子的最高占据分子轨道（Highest occupied molecular orbital，HOMO）和最低未占分子轨道（Lowest unoccupied molecular orbital，LUMO）的能级为主要依据，也会引入界面调控和能级隧穿效应等策略。一般情况下，HOMO能级越高，LUMO能级越低，都会有利于正负极的载流子注入；而这与宽禁带（HOMO能级低和LUMO能级高）的矛盾则较为显著，使得注入过程中容易出现激子复合区变宽或偏离发光层等问题，激基复合物和激基缔合物常常作为蓝紫光化合物器件的伴生产物。另外，为了实现更有效的载流子注入，器件优化上会采用合适的能级设计来增加有效注入，但会导致器件的开启电压相对较高。采用D-A基团辅助的双极性材料体系可以在一定程度上利用增宽氧化还原分布的方式缓解载流子注入的问题，但是引入的分子内电荷转移（Intramolecular charge transfer，ICT）效应也会在一定程度上引发光色红移、光谱变宽、分子前线轨道重叠降低（效率降低）等现象。因此，如何平衡各因素就成为目前蓝紫光材料研究优化的热点，暂时并没有一个特别有效的策略解决上述问题。对于载流子的传输，通常与分子固有结构、堆积形式和固定取向相关，其更多的是依赖对其聚集态行为的调控，也是目前分子设计中较为活跃的研究方向。例如，目前认为线性结构更加有利于实现平面有序堆积而减小载流子跳跃势垒，优势取向也更加有利于光学输出等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；但是，这些都会在一定程度上增加分子在聚集态下的耦合。因此，在分子设计层面需要更加精准的设计，对于光色和最终器件性能还是多以结果导向分析为主。经过近二十年的优化，大家普遍认为在构筑D-A体系时，较弱或较为中和的构筑基元可能在蓝紫光材料能级设计上更具优势。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第三，器件结构的优化与选择：不同于其他光色材料，蓝紫光材料对于器件的敏感度相对较强，不仅是对载流子注入/传输层的能级结构有挑剔性，甚至对于其传输载流子的效率和机制存在一定要求——这主要是由于更多的电致发光的功能辅助必须依赖于它们，蓝紫光的发光层所能承载的功能不多。" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（c）为有机电致发光二极管的常见结构，科学工作者起初的研究还集中在如何提高发光层的功能性方面，赋予其载流子注入传输特性等，但很快发现这类材料的效率总是达不到理想的程度，特别是一些激子利用率极高、材料固态发光效率极好的体系，却在综合性能上逊色许多；后来，大家普遍改变了这样的研究策略，回归到单一发光的结构设计道路上。另外，器件结构优化中，可以为蓝紫光提供有效的载流子注入的体系并不是特别多" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。例如，空穴方向的4,4',4″-三（咔唑-9-基）三苯胺（4,4',4″-Tris（carbazol-9-yl）triphenylamine，TcTa）、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲（Dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile，HAT-CN）等，电子方向的1,3,5-三（1-苯基-1" }, { "name": "italic", "data": [ { "name": "text", "data": "H" } ] }, { "name": "text", "data": "-苯并咪唑-2-基）苯（2,2',2″-（1,3,5-Benzinetriyl）-tris（1-phenyl-1-" }, { "name": "italic", "data": [ { "name": "text", "data": "H" } ] }, { "name": "text", "data": "-benzimidazole），TPBi）等，更多的功能层结构被期待。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第四，在评价有机发光材料的性能时，除了光致发光量子产率（Photoluminescence quantum yield，PLQY）、电致发光峰位（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "）、外量子效率（External quantum efficiency，EQE）、色坐标（Commission internationale de l'Eclairage，CIE）、光谱半峰全宽（Full width at half maxima，FWHM）等参数外，越来越多的研究者开始关注有机发光材料的耐久性" }, { "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": "。尽管OLED的应用已经普及到人们生活的方方面面，但需要发展更多兼具高效率与长寿命的有机发光材料。目前，要获得长寿命的OLED材料，必须从两个角度考虑。从材料角度分析，杂原子的引入能够有效地调节碳氢骨架的电子分布而实现更高的电致发光效率，但目前的研究显示这种杂原子在器件寿命上表现不是十分理想。例如，氟原子能够显著降低电子的注入势垒，但C—F键的极性容易导致二者的异裂而化学稳定性下降" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。从器件的角度，为了提高激子利用率，往往会设计反系间窜越通道以利用三线态激子，而三线态激子的积累会引起激子和极化子猝灭影响使用寿命。例如，热活化延迟荧光（Thermally activated delayed fluorescence，TADF）体系下，限制激子浓度是目前提高器件稳定性的研究热点" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于此，对于具有更高能级的蓝紫光材料，这些问题都是更加绕不开的瓶颈，需要更多可参考的理论指导。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "以上陈述从材料设计的角度相对系统地区分了电致发光中激子生成和激子分配两个过程对于其效率影响的因素，总结了OLED发光材料设计与器件制备、优化面临的四个关键科学问题。另外，红、黄、绿、天蓝等光色有机发光材料正在齐头并进、迅猛发展，为了实现电致发光领域中的“百色齐放”，研究者们开发了众多新型紫外/深蓝荧光发光基元，开创了不同的发光机制，为推进实现高效、稳定的紫外/深蓝OLED完成了大量的数据积累。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　蓝紫光有机发光材料" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　蓝紫光有机发光材料分类" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "有机发光材料根据光致发光机制的差异可分为荧光材料和磷光材料，前者是指分子受激跃迁后得到自旋方向不变的激子（单线态激子），而后者则是通过ISC过程获得自旋方向改变的激子（三线态激子）。但是，磷光这种辐射跃迁过程通常是禁阻的，必须要借助一些特殊结构和机制完成。例如，常见的铱类配合物就是依靠重金属的耦合效应完成的，特别是当氧气不存在时，发光通常都会显著增强，是比较典型的磷光化合物。而在电致发光中，发光材料的划分也基本延续了这个概念，只不过三线态激子并非只来源于单线态转化，而更多来源于载流子注入和复合，而且生成几率也有了很大的提高。 对于蓝紫光化合物来讲，由于磷光材料很难达到如此高的三线态能级，所以材料种类并不常见，仅是Holmes等在2005年报道了一组铱配合物异构体蓝光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，基于" }, { "name": "italic", "data": [ { "name": "text", "data": "fac" } ] }, { "name": "text", "data": "⁃Ir（pmb）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "与" }, { "name": "italic", "data": [ { "name": "text", "data": "mer" } ] }, { "name": "text", "data": "⁃Ir（pmb）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的OLED的电致发光主峰位分别在389 nm和395 nm，外量子效率仅为2.6%和5.8%，未能达到常见纯有机骨架的材料体系的电致发光性能。事实上，基于高效RISC过程的CH类共轭材料展现出更大的应用潜质，无论是三线态⁃三线态湮灭（Triplet⁃triplet annihilation，TTA）类材料，还是热活化延迟荧光材料和“热激子”材料，都有不俗的表现。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "因此，我们依据发光机制，将材料划分为磷光、传统荧光、三线态-三线态湮灭、热活化延迟荧光、“热激子”材料，增补介绍了含有聚集诱导发光特性以及含多重共振结构的材料。由于传统荧光材料数量较多，因此从基元入手，列举了目前比较活跃且有潜力的几个核心结构；另外，目前较为活跃的材料设计理论中，优选在蓝紫光材料构筑中较有优势的“热激子”理论和“杂化激发态”策略，展示目前其在高色纯度材料构筑中的优势；最后根据个人理解，简单分析了目前激子能级调控策略的发展方向。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　传统荧光材料" } ], "level": "2", "id": "s3b" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.1　蒽基" } ], "level": "3", "id": "s3b1" } }, { "name": "p", "data": [ { "name": "text", "data": "有机材料的电致发光最早是由Pope等于1963年在蒽晶体中发现的" }, { "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": "，蒽类材料具有较高的荧光量子产率、较好的成膜性，这都有利于OLED的制备。蒽的平面结构容易引起聚集结晶，常通过化学修饰来避免结晶问题。蒽是常用的蓝光材料构筑基元，MADN、TMADN等已经商业化的蓝光材料均是基于蒽设计合成的，这些蓝光材料均具有较好的稳定性以及较高的荧光量子产率。" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "展示了部分基于蒽的紫外/深蓝光传统荧光材料。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "基于蒽的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 2" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on anthracene" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941916&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941923&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941919&type=", "width": "75.25653076", "height": "46.80035400", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为了避免聚集结晶或荧光猝灭，通常会引入大空间位阻的基团构筑扭曲的分子构象，打破蒽的平面性，同时提高热稳定性与成膜性。2011年，张晓宏课题组报道了一种深蓝光材料BPPA的电致发光性能" }, { "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": "。在蒽的9号位和10号位分别引入叔丁基修饰的二苯基取代苯，设计合成了非平面性分子BPPA。得益于多构象性，BPPA具有很好的热稳定性，其" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "=207 ℃。基于BPPA的OLED的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.2%，电致发光峰位在430 nm，半峰宽为55 nm，色纯度较高，其电致发光光谱在不同电压下保持一致，光谱稳定性较好。2013年，Kim课题组设计合成了一种不对称蒽衍生物TPAXAN" }, { "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": "。在蒽的9号位和10号位分别引入萘和二甲基苯形成不对称的分子构象，引入三苯胺进一步增加分子扭曲程度，避免了荧光猝灭。基于TPAXAN的OLED呈现深蓝光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=4.62%，电致发光峰在428 nm，相应的CIE坐标为（0.16，0.05）。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "基于蒽的深蓝光材料不仅具有优异的电致发光性能，还具有较好的主体应用潜力。2015年，焦博课题组设计合成了一系列氟原子修饰的蒽型蓝光材料" }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "F-DPA（" }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "=2，3，4）" }, { "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": "。通过在蒽衍生物的不同位点引入氟原子，得到了一系列性能优异的深蓝光材料。C—F键具有较低的HOMO能级，引入氟原子能够改善材料的吸电子能力。基于" }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "F-DPA的OLED在420 nm与435 nm处均存在两个强度相当的发射峰，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为2.64%、2.53%、 2.99%。以4F-DPA 作为主体、以天蓝光传统荧光材料DPAVBi作为客体制备了OLED，其外量子效率最大值为3.4%。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.2　芘基" } ], "level": "3", "id": "s3b2" } }, { "name": "p", "data": [ { "name": "text", "data": "芘是一种具有高载流子迁移率和良好化学稳定性的蓝光发色团，在水溶液中能够生成激基复合物，具有较高的荧光量子产率，过去常被应用于荧光标记" }, { "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": "。芘在薄膜状态下具有强烈的结晶倾向，这对于制备OLED器件是非常不利的，芘基材料在薄膜状态下容易生成激基缔合物，导致发光红移以及发光效率降低" }, { "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": "。常通过引入较大的刚性基团阻止芘单元之间的强相互作用、破坏芘的结晶倾向以及抑制激基复合物的形成，大的刚性基团能够增加分子尺寸、提高热稳定性，扭曲的分子构象也能够抑制共轭程度延长、避免荧光猝灭。" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "展示了部分基于芘的紫外/深蓝光传统荧光材料。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "基于芘的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 3" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on pyrene" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941925&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941932&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941927&type=", "width": "73.58020020", "height": "64.03265381", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2013年，Kaafarani课题组报道了以四氢芘为核心的蓝紫光材料（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）、（b））的电致发光性能" }, { "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": "。基于" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）、（b）的OLED均实现了深蓝光发射，电致发光峰位分别在422 nm与425 nm，相应的CIE坐标分别为（0.16, 0.05）与（0.19, 0.08）。由于载流子的注入与传输不平衡，导致两组OLED的效率较低、色纯度较差，启亮电压均在5 V以上，电流效率非常低，仅有0.02 cd·A" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "和0.07 cd·A" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。基于" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（b）的OLED的电致发光光谱在600 nm之后存在长波长发光。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2015年，徐晨课题组报道了一种基于芘的紫外发光材料DPPP的电致发光性能" }, { "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": "。为了保护芘基，避免分子在聚集态下π-π堆积，在芘核两侧引入两个庞大的三苯基取代苯，大空阻基团的引入不仅抑制了激基缔合物的形成同时保留了芘高荧光量子产率的特性，实现了高色纯度的紫外发光。基于DPPP的OLED，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 2.2%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=396 nm，相应的CIE坐标为（0.16, 0.04）。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2020年，廖良生课题组将芘引入到螺芴吖啶的不同位点上，得到了三种深蓝光材料TFPy2、 TFPy3和TFPy4" }, { "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": "。芘基团能够提供高的荧光量子产率，三种材料掺杂薄膜的PLQY均在60%以上；螺芴吖啶是一个大空间位阻的刚性基团，引入螺芴吖啶提高了材料的热稳定性，三种材料的" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "均在150 ℃以上。基于三种材料制备的OLED均实现了深蓝光发射，其电致发光峰位分别为414，406，404 nm，相应的CIE坐标分别为（0.15，0.03）、（0.16，0.02）、（0.16，0.02），EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为3.8%、4.8%、5.1%。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.3　芴基" } ], "level": "3", "id": "s3b3" } }, { "name": "p", "data": [ { "name": "text", "data": "芴作为桥连联苯的重要衍生物，具有高固态荧光量子产率以及较好的修饰位点，是一种非常有潜力的蓝紫光基元。未经修饰的芴的晶体具有紫色荧光，在薄膜状态下，其平面刚性的结构容易诱导激基复合物或者芴酮生成，产生长波长发光，影响器件的电致发光效率以及色纯度。为了避免这个问题，通常在芴基上引入空间位阻较大的基团来抑制激基复合物或芴酮的生成。" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "展示了部分基于芴的紫外/深蓝光传统荧光材料。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "基于芴的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 4" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on fluorene" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941933&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941940&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941938&type=", "width": "154.33624268", "height": "114.00067139", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2003年，Okumoto等报道了一种芴为发光核心的近紫外材料F" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PA的电致发光性能" }, { "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": "。基于F" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PA的OLED的电致发光峰在405 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 1.95%，以F" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PA作为磷光材料的主体的OLED也实现了较好的效率以及较低的滚降。2008年，马於光课题组报道了一种以芴基深蓝光材料T4搭配黄光材料Rubrene作为发光层的双层白光OLED，成功实现了白光发射，证明了芴基紫外材料在白光OLED中的潜在应用" }, { "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": "。2015年，周卓辉课题组设计合成了两种含氰基修饰的芴基发光材料C3FLA-2和C2FLA-1" }, { "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": "。分别制备了基于C3FLA-2和C2FLA-1的OLED，基于C3FLA-2的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=416 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 6.5%的电致发光，基于C2FLA-1制备的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=392 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=3.5%的电致发光。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "作为芴基的重要衍生基元，螺芴由于具有正交螺旋连接和刚性结构，具有较宽的带隙以及较好的热稳定性。其中，螺双芴是一种以电子传输占优势的基团，具有较高的电离电位，用于制备OLED时易导致较高的启亮电压和较低的效率。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "为了更好地发挥螺芴用于构筑蓝紫光材料的优势，解决螺芴类蓝紫光材料载流子注入与传输困难的问题，降低器件的启亮电压，研究者们做出了许多研究。早在2005年，吴忠帜课题组就设计合成了一系列二聚螺芴衍生物，基于B2、T2、TB2等二聚螺芴衍生物制备的OLEDs电致发光峰均在374~402 nm之间，EQE最高能达到3.6%，但这些器件在低亮度下的电压很高、效率滚降很大" }, { "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": "。2006年，Etori等设计合成了一系列基于螺双芴的蓝紫光材料TSBFB、BSBFB、1SBFN、2SBFN，基于该系列材料的OLED均实现了蓝紫光发射，启亮电压均在7~8 V，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "在2%~3%范围内" }, { "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": "。2009年，Cocherel等报道了一种螺芴衍生物DSX-IF的电致发光性能，基于DSX-IF的OLED电致发光峰位为414 nm, 启亮电压高达10 V，最大电流效率仅有0.6 cd·A" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "咔唑类化合物具有较好的空穴传输能力，引入咔唑基团能够改善螺芴类材料的载流子传输。2007年，马於光课题组在螺双芴上引入烷基链和咔唑基团设计合成了深蓝光材料TCPC-6" }, { "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": "。TCPC-6具有较好的热稳定性以及空穴传输性能，以TCPC-6为发光层的OLED实现了深蓝光发射，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=3.72%，该器件的启亮电压在4 V左右，与以往基于螺芴类材料的OLED相比有所改善，但与基于其他发光材料的蓝紫光OLED相比仍偏高。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "D-A构型有利于改善载流子的注入和传输，双极传输特性对于提高材料的电致发光性能至关重要。2012年，许辉课题组设计合成了两种以螺双芴为发光核心的不对称D-π-A构型的双极传输蓝紫光材料" }, { "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": "。基于9DPNAFSPO与9TPAFSPO的OLED的启亮电压分别为3.1 V和3.3 V，均实现了深蓝光发射，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为407 nm和424 nm，相应的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为1.96%和2.71%。值得一提的是，9DPNAFSPO的PLQY相对于大部分深蓝光材料偏低，但其双极传输性能弥补了低PLQY带来的电致发光效率损失。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2014年，孙岳明课题组设计合成了近紫外发光材料SF-DPSO，并进一步拓展了螺芴类蓝紫光材料的应用" }, { "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": "。SF-DPSO中大空阻的螺双芴基团以及两个可自由旋转的苯桥基，使得材料具有非常扭曲的空间构象以及极好的热稳定性能。基于SF-DPSO制备的OLED的启亮电压较高，在6 V左右，电致发光峰在402 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "仅有0.2%，这可能与载流子注入与传输不佳有关。以SF-DPSO分别作为蓝色磷光材料FIrpic和绿色磷光材料Ir（mppy）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的主体，制备的OLED分别实现了EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=6.8%和EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=8.8%的电致发光。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "引入杂原子也是调控分子性能的一种手段，例如通过调整硫原子的价态可以实现对分子的共轭长度以及平面性的调控。2015年，苏仕健课题组将硫原子引入螺芴，得到了四种具有不同电致发光性能的蓝紫光材料" }, { "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": "。其中，基于CzB-S与TPA-S的OLED分别实现了近紫外发射和深蓝光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为2.03%与1.76%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "除了小分子的芴基材料以及螺芴类材料外，聚芴类材料也可以用于实现蓝光发射。一方面聚合物的分子结构能够抑制激基缔合物的形成，另一方面聚合物可能存在载流子传输通道，有利于载流子的传输。2007年，Liu 等设计合成了一系列六臂星型芴基寡聚物材料" }, { "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": "。基于T2、T3、T4分子的OLED均实现了深蓝光发射，以T2作为主体制备的磷光器件，其亮度和效率都优于以商业化主体材料聚乙烯咔唑作为主体的磷光器件。2010年，裴坚课题组设计了一系列以三聚茚为核心的三维共轭芴基寡聚物材料" }, { "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": "。其中，基于sFOMe、sFCbz、sFTaz、sFOxd四种材料的OLED均实现了深蓝光发射，基于四种材料的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为426，426，428，430 nm，相应的电流效率分别为0.39，0.43，0.80，0.56 cd·A" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。2012年，王志明等报道了一系列菲并咪唑与芴偶联的深蓝光共轭聚合物的电致发光性能" }, { "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": "。菲并咪唑的引入改善了聚芴的热性能以及载流子传输性能，其中，基于P3/4的OLED电致发光峰位在425 nm，相应的CIE坐标为（0.17，0.08）。2020年，Therdkatanyuphong等报道了一系列以螺双芴衍生基团为核的咔唑低聚物" }, { "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": "。通过溶液加工制备的基于2,7-CSF、2,7-CSFX、2,7-CSBF三种材料的OLED均实现了深蓝光发射，相应的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为1.71%、2.07%、2.49%。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.4　咔唑基" } ], "level": "3", "id": "s3b4" } }, { "name": "p", "data": [ { "name": "text", "data": "咔唑类化合物由于具有较好的空穴传输能力、无定型成膜性和易修饰等特点而广泛地应用到蓝光材料中。咔唑是一个弱的电子给体基团，易于修饰，咔唑的平面和刚性具有较高的光致发光量子产率，咔唑具有高三线态能级，有利于构筑蓝紫发光材料。" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "展示了部分基于咔唑的紫外/深蓝光传统荧光材料。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "基于咔唑的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 5" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on carbazole" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941943&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941949&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941946&type=", "width": "75.58618164", "height": "112.64111328", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2008年，支志明课题组设计合成了两种新型星型咔唑衍生物MTPC-Me和MTPC-Et" }, { "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": "。基于MTPC-Me的OLED的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=1.2%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=396 nm，以MTPC-Me作为空穴传输层制备了以Alq" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " 为发光层的OLED，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=1.2%。2010年，连加荣等通过改善器件结构将MTPC-Me和MTPC-Et的电致发光效率进一步提高" }, { "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": "。基于MTPC-Me和MTPC-Et的OLED均实现了深蓝光发射，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "均在406 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为2.6%和3.3%，基于两种材料的OLED的电致发光光谱在493 nm处均存在发光层与电子传输层的复合发光峰。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "通过在咔唑上取代不同的官能团，可以实现不同的光物理和电致发光性能。2011年，Jabbour课题组在中心咔唑基团上引入苯并咪唑，设计合成了近紫外光材料Cz-2pbb，并基于Cz-2pbb制备了高效、色稳定的白光器件" }, { "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": "。基于Cz-2pbb的单色光OLED呈现近紫外发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=410 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.9%。以Cz-2pbb作为主体，同时掺杂红光磷光和绿光磷光材料制备了单层白光OLED，EQE最高可以达到17.5%，同时8 V电压下其显色指数（CRI）可以达到82，实现优异的白光发射与Cz-2pbb较好的双极传输能力密不可分。2016年，王世荣课题组报道了一种深蓝光材料CzB-PIM的电致发光性能" }, { "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": "。通过联苯桥连接电子给体咔唑、电子受体三苯基咪唑，并在咪唑N1、C4、C5号位引入苯基增加分子的扭曲程度。基于CzB-PIM的OLED的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=420 nm，相应的CIE坐标为（0.17，0.06），电流效率最大值为2.3 cd·A" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。2017年，Joseph等在中心咔唑上分别引入苯基、芴基、咔唑、三苯胺等基团设计合成了一系列蓝紫光材料" }, { "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": "。其中，基于4（a）~（d）和4（e）的OLED均实现了深蓝光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别能达到1.7%、2.9%、2.5%、2.1%和3.1%，其中，取代基为咔唑的4c分子的激发态属于局域态和电荷转移态的杂化态，咔唑的取代促进了杂化态的形成。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "溶液加工具有柔性、低成本、可旋涂、高速的优点，溶液加工与真空沉积是制备OLED常用的两种方法。2018年，Jou等设计合成了一种基于咔唑的深蓝光发光材料JV55" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过溶液加工制备的基于JV55的一系列掺杂器件的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "在423~418 nm之间，EQE能达到6.5%。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.5　菲并咪唑" } ], "level": "3", "id": "s3b5" } }, { "name": "p", "data": [ { "name": "text", "data": "在众多CH骨架的蓝紫光材料体系的修饰改性优化中，菲并咪唑结构异军突起，成为了蓝紫光构筑基元的新宠。它由强荧光的生色团菲以及具有非线性光学性质的咪唑组成，并含有高度共轭的大π键，能够形成平面结构，展现为一个弱电子给体和电子受体双重特性。2011年，王志明等设计合成了菲并咪唑（PI），并首次指出菲并咪唑是非常具有潜力的深蓝光发光核心" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。PPI非掺杂薄膜的光致发光峰在395 nm，且半峰宽小于50 nm；基于PPI的OLED最高EQE能达到1.86%，电致发光峰在412 nm" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "展示了部分基于菲并咪唑的紫外/深蓝光传统荧光材料。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "基于菲并咪唑的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 6" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on phenanthroimidazole" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941952&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941959&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941954&type=", "width": "163.00000000", "height": "94.44006348", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为了提高发光效率，2013年，路萍课题组在PPI上引入咔唑基团设计合成了深蓝光材料M1和M2" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。M1与M2的热稳定性和载流子传输性能相对于PPI也均显著提高，M1的" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "=132 ℃，M2的" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "高达207 ℃，M2具有双极传输特性，这有利于提高OLED的发光效率。基于M1和M2的OLED 最高EQE分别为1.94%和3.02%，与PPI相比，M1与M2电致发光峰位发生红移，分别为420 nm和428 nm。随后，该课题组在PPI中引入位阻更大的三苯基硅烷设计合成了深蓝光材料SiPIM" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。引入四面体几何结构的三苯基硅烷，增加了分子的空间体积，避免了分子密堆积引起的荧光猝灭，三苯基硅烷的引入没有显著增加共轭长度，保持了PPI的蓝紫发光特性。基于SiPIM分别通过真空沉积和溶液加工制备了OLED，均呈现深蓝光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为6.29%和2.40%，相比于PPI效率显著提高。2016年，该课题组在菲并咪唑的C2号位引入萘基设计合成了深蓝光材料PIMNA，并进一步拓展了基于菲并咪唑的蓝紫光材料的相关应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "59", "type": "bibr", "rid": "R59", "data": [ { "name": "text", "data": "59" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。PIMNA兼具良好的热稳定性和高荧光量子产率，基于PIMNA的OLED电致发光峰在412 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 2.43%。虽然PIMNA并不能作为普遍应用的主体材料，但是以深蓝光材料PyINA作为发光客体、以PIMNA作为主体制备的OLED，与使用商业化主体DPEPO制备的OLED相比，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "高出近40%，这表明PIMNA在OLED主体材料方向上有一定的应用潜力。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "与此并行，从2012年起，佟庆笑课题组报道了一系列基于菲并咪唑的深蓝光发光材料。例如，在菲并咪唑上的不同位点引入三苯胺，设计合成了PATPA和BPA-BPI" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "60", "type": "bibr", "rid": "R60", "data": [ { "name": "text", "data": "60" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于PATPA与BPA-BPI分别制备了OLED，均呈现出深蓝发射，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别在424 nm 与428 nm，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为0.72%和1.37%。为了提高热稳定性以及抑制分子聚集猝灭，2013年，该课题组在菲并咪唑上引入体积庞大的多环芳香烃设计合成了深蓝光材料TTP-TPI" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "61", "type": "bibr", "rid": "R61", "data": [ { "name": "text", "data": "61" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于TTP-TPI的OLED最高EQE为5.02%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=424 nm，相应的CIE坐标为（0.16，0.05）。为了实现更优异的电致发光性能，2014年，该课题组报道了一种调控分子聚集的“交错面对面”堆积策略" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "62", "type": "bibr", "rid": "R62", "data": [ { "name": "text", "data": "62" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过甲基修饰的苯桥基对位连接两个菲并咪唑基团，设计合成了船型深蓝光材料XBTPI。XBTPI具有较好的载流子迁移率，同时保留了菲并咪唑的深蓝发光特性。基于XBTPI的OLED实现了深蓝光发射，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=4.93%。2015年，该课题组采用间位连接策略设计合成了蓝紫光材料m-BBTPI" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "63", "type": "bibr", "rid": "R63", "data": [ { "name": "text", "data": "63" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。相比于对位连接的同分异构体，m-BBTPI的光致发光光谱峰位蓝移了16 nm。基于m-BBTPI的OLED实现了深蓝光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "= 3.63%。2016年,该课题组通过在螺芴上引入菲并咪唑和三苯胺，合成了不对称菲并咪唑衍生物PPI-F-TPA，并进一步拓展了基于菲并咪唑的深蓝光材料的应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "64", "type": "bibr", "rid": "R64", "data": [ { "name": "text", "data": "64" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于PPI-F-TPA的OLED，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=3.11%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=425 nm，相应的CIE坐标为（0.16, 0.05）。以PPI-F-TPA作为主体，分别制备了绿光和橙红光磷光OLED，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别达到了15.6%和12.5%，并且在高亮度下展现出较低的效率滚降。PPI-F-TPA具有优异的双极传输性能和低滚降的电致发光性能，作为主体材料应用于磷光器件时具有一定的优势。2016年，其合作伙伴李振声教授课题组在叔丁基修饰的菲并咪唑上引入咔唑，设计合成了深蓝光材料PIBCz" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "65", "type": "bibr", "rid": "R65", "data": [ { "name": "text", "data": "65" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。刚性咔唑基团的引入一方面使得PIBCz具有良好的热稳定性，其" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "=174 ℃，另一方面有效限制了分子内电荷转移作用。基于PIBCz的OLED最高EQE为2.74%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=414 nm，相应的CIE坐标为（0.15，0.05）。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "作为蓝紫光的新宠，菲并咪唑虽然在很多材料体系中展现出更高的效率和色饱和度，但是其严重的拖尾现象对于其提高色纯度提出了不小的挑战。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2.6　其他构筑基元" } ], "level": "3", "id": "s3b6" } }, { "name": "p", "data": [ { "name": "text", "data": "除了蒽、芘、芴、咔唑、菲并咪唑之外，许多基于其他构筑基元的紫外/深蓝光传统荧光材料也展现出优异的电致发光性能，如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "所示。2010年，Park等设计合成了一系列以吡嗪为发光核心的蓝紫光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "66", "type": "bibr", "rid": "R66", "data": [ { "name": "text", "data": "66" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过调整取代位置改变了分子的共轭长度，得到三种性能优异的蓝光材料。其中邻位取代和对位取代的吡嗪及衍生物" }, { "name": "italic", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "-TP-EPY和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-TP-EPY为深蓝光材料。基于" }, { "name": "italic", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "-TP-EPY和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-TP-EPY的OLED的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别在419 nm和423 nm，相应的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为1.27%和1.88%。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "基于其他构筑基元的紫外/深蓝光传统荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 7" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue traditional fluorescence materials based on other building blocks" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941961&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941964&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941962&type=", "width": "160.62286377", "height": "92.73284912", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2012年，吴朝新课题组通过在三苯胺上引入不同的含氟取代基，设计合成了一系列以三苯胺为发光核心的蓝紫光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "67", "type": "bibr", "rid": "R67", "data": [ { "name": "text", "data": "67" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。引入强吸电子基团能够降低HOMO和LUMO能级，降低空穴迁移率实现电荷转移平衡，同时增加分子间相互作用力，提高材料稳定性。通过调整不同的取代基以及取代位点，得到了一系列电致发光性能不同的蓝紫光材料。其中，具有强分子内相互作用的TPA-（2）-F以及具有刚性结构、大空阻TPA-（3,5）-CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "具有高于其他材料的熔点，TPA-（3）-F、TPA-（4）-F、TPA-（2,4）-F的" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "较低，在59~73 ℃之间。基于该系列三苯胺衍生物的OLED的电致发光峰位在408~428 nm之间，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "在0.43%~0.60%之间。引入强吸电子基团—CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "使得TPA-（3,5）-CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的HOMO能级最低，但也避免了薄膜状态下分子的密堆积，基于TPA-（3,5）-CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的OLED外量子效率最高。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2013年，李振声课题组在中心砜基上引入咔唑，设计合成了两种深蓝光材料CzS1和CzS2" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。得益于D-π-A-π-D的分子构型，CzS1和CzS2均具有较好的热稳定性。给体咔唑与受体砜之间形成弱的ICT作用，自由旋转的苯环限制了分子共轭程度的延伸。基于CzS1和CzS2的OLED均实现了深蓝光发射，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为426 nm和417 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为4.21%和2.70%，高EQE源于高光致荧光量子产率以及双极传输能力。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "具有宽禁带的四苯基硅烷是蓝紫光材料的优异构筑基元。2014年，路萍课题组设计合成了一系列以四苯基硅烷为核心、不同基团修饰的近紫外材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "69", "type": "bibr", "rid": "R69", "data": [ { "name": "text", "data": "69" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。四苯基硅烷的大体积以及硅原子之间的相互作用削弱了ICT作用。其中，CzPySiSF不存在分子间的电荷转移，这是因为咔唑、吡啶、螺芴等富电子基团的引入平衡了四苯基硅烷宽带隙对电子注入造成的不利影响。基于CzSiSF、PySiSF和CzPySiSF三种材料的OLED的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为410，412，408 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为0.59%、0.48%和0.31%。其中，基于CzSiSF和PySiSF的OLED电致发光光谱均存在传输层与发光层界面复合发光产生的长波长发光，长波长处的发射降低了电致发光效率和色纯度，而具有双极传输特性的CzPySiSF 电致发光光谱上没有多余发光峰。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2014年，魏斌课题组报道了一种以芳胺为核、接咔唑修饰的星型近紫外光材料SSM" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "70", "type": "bibr", "rid": "R70", "data": [ { "name": "text", "data": "70" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于SSM的OLED，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=408 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.56%。以SSM做主体、蓝色荧光材料DSA-ph为客体制备了OLED，与以CBP做主体、DSA-ph做客体的OLED相比，SSM扭曲的构象抑制了激基复合物生成，抑制了电致发光光谱的长波长发射和肩峰发射，有效地提高了色纯度、降低了CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "值，提高了电致发光效率。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2015年，肖立新课题组报道了一种以1,2-苯并菲为核心的深蓝光材料的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "71", "type": "bibr", "rid": "R71", "data": [ { "name": "text", "data": "71" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在1,2-苯并菲的6号位和12号位分别引入咔唑设计合成了深蓝光材料BPCC。咔唑的引入使得BPCC具有较好的热稳定性，其" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g " } ] }, { "name": "text", "data": "=181 ℃，同时也抑制了分子密堆积。基于BPCC的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=416 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=4.9%电致发光。 4" }, { "name": "italic", "data": [ { "name": "text", "data": "H" } ] }, { "name": "text", "data": "⁃1,2,4⁃三唑（4" }, { "name": "italic", "data": [ { "name": "text", "data": "H" } ] }, { "name": "text", "data": "⁃1,2,4⁃triazole，TAZ）具有较好的吸电子效应，3,4,5⁃三苯基⁃4" }, { "name": "italic", "data": [ { "name": "text", "data": "H" } ] }, { "name": "text", "data": "⁃1,2,4-三唑是常用的电子受体基团。2018年，李峰课题组通过在三唑上引入不同数量的三苯胺基团设计合成了一系列深蓝光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "72", "type": "bibr", "rid": "R72", "data": [ { "name": "text", "data": "72" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，基于4NDTPA⁃TAZ的OLED实现了深蓝光发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=426 nm，相应的CIE坐标为（0.16, 0.04），EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为6.3%。该文章作者认为高的EQE源于三线态⁃极化子相互作用（Triplet⁃polaron interaction，TPI），TPI过程可以产生多余的单线态，磁电导效应（Magneto⁃current，MC）证明了TPI过程的发生。2018年，薛善锋课题组采用三唑作为给体、三苯胺作为受体设计合成了深蓝光材料TPATZ，基于TPATZ的OLED，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=430 nm，相应的CIE坐标为（0.16, 0.05），EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为5.92%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "73", "type": "bibr", "rid": "R73", "data": [ { "name": "text", "data": "73" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　三线态‐三线态湮灭" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "具有三线态-三线态湮灭特性的荧光材料理论上可以达到62.5%的激子利用率。两个三线态激子湮灭形成一个中间态，这个中间态最终转变成一个单线态激子，单线态激子辐射跃迁发出荧光。" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "展示了部分具有TTA特性的深蓝光材料。2014年，Pu课题组设计合成了一系列具有优异电致发光性能、高热稳定性的双蒽衍生物，包含非D-A构型的BD1、弱D-A构型的BD2以及D-A构型的BD3" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "74", "type": "bibr", "rid": "R74", "data": [ { "name": "text", "data": "74" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于BD1与BD2的OLED均实现了深蓝光发射，其电致发光峰位分别在424 nm与430 nm，光谱半峰宽分别为44 nm和47 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别达到了8.9%与9.5%。值得一提的是，以BD3作为发光客体的OLED电致发光峰位在432 nm，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=12%。实现如此高效的蓝光发射，首先与分子结构密不可分，蒽是优异的蓝光材料构筑基元，D-A构型促进了载流子的注入与传输；其次，掺杂发光层中存在主体向客体的能量转移；最后，高掺杂浓度下存在客体直接捕获载流子，电致发光中BD3存在三线态-三线态湮灭的激子利用过程，使得部分三线态激子能够用于发光。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "具有TTA特性的深蓝光荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 8" } ], "title": [ { "name": "text", "data": "Molecular structures of deep-blue fluorescence materials with TTA characteristic" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941966&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941970&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941968&type=", "width": "76.01507568", "height": "72.79669189", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "目前，性能优异的具有TTA特性的发光材料其电致发光过程中常常伴随其他的三线态激子利用通道。2018年，王磊课题组设计合成了两种具有TTA特性的蓝光材料3CzAnBzt和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt，基于两种材料的OLED均实现了高的EQE以及较小的滚降，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为10.06%和9.23%。此外，3CzAnBzt和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt 均存在单线态S" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "m" } ] } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "≥1）与高能级三线态T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "＞1）之间能级差可忽略的情况，这有利于实现更好的TTA过程" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "75", "type": "bibr", "rid": "R75", "data": [ { "name": "text", "data": "75" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2021年，王磊课题组设计合成了两种蓝光材料2M-ph-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt和2M-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt。其中，2M-ph-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt的激发态具有HLCT性质，能够通过TTA和高能级的反系间窜跃（High-level reverse intersystem crossing，hRISC）过程获得额外的单线态激子，基于2M-ph-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt制备的OLED的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为10.44%；而2M-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt电致发光中TTA过程占主导位置，其激子利用率受限，基于2M-" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "CzAnBzt制备的OLED的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "为8.08%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "尽管在近十年来报道的TTA机制的蓝紫光体系不多，但是大部分RISC的过程中都不可避免地存在该机制的辅助。从构筑TTA类材料设计指导原则上，并没有特别的规律，但是含有蒽基和芘基的材料中TTA组分可能更多一些，从而导致该类基元通常作为提高激子利用率的重要候选基元" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "77", "type": "bibr", "rid": "R77", "data": [ { "name": "text", "data": "77" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.4　热活化延迟荧光材料" } ], "level": "2", "id": "s3d" } }, { "name": "p", "data": [ { "name": "text", "data": "TADF材料是指通过合理的分子设计强化T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "→S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的RISC并与S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "→T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的ISC过程形成有效的竞争，促使电致发光过程中更多的三线态激子跃迁到单线态；通过高效地捕获三线态激子，可以使得激子利用率理论上达到100%。事实上，从目前已报道的光物理数据和器件结果上看，TADF机制在提高OLED性能上的贡献是显著的，因此，其也被称为“第三代OLED技术”的典型代表。但是，由于TADF材料在构筑高能的T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级上略显乏力，而且三线态激子的湮灭状况也会随着能级的增高而变得更为严重，所以典型TADF类蓝紫光材料并不是十分常见。" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "展示了紫外/深蓝光热活化延迟荧光材料。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "紫外/深蓝光热活化延迟荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 9" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue TADF materials" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941971&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941973&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941972&type=", "width": "77.85833740", "height": "60.60479736", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2012年，Adachi课题组报道了一种深蓝光TADF材料CZ-PS的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在砜上引入叔丁基修饰的咔唑基团，设计合成了深蓝光材料CZ-PS。基于CZ-PS的OLED 电致发光峰在420 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=9.9%。受该工作" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "启发，2020年，卢志云课题组报道了首例紫外TADF材料的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "79", "type": "bibr", "rid": "R79", "data": [ { "name": "text", "data": "79" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于CZ-MPS的OLED电致发光峰位在389 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=9.3%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2021年，Kim 等在前期赵祖金教授报道的聚集诱导延迟荧光（Aggregation induced delayed fluorescence，AIDF）工作" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "80", "type": "bibr", "rid": "R80", "data": [ { "name": "text", "data": "80" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "的启发下，报道了基于TB-tCz和TB-tPCz的深蓝光OLED材料及器件，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为412 nm和420 nm，半峰全宽分别为44.2 nm和43.5 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为15.9%和14.1%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。该作者指出,实现如此高效、高色纯度的深蓝光发射，一方面是因为TADF材料能够实现快速的RISC，实现对三线态激子的高效利用;另一方面是因为聚集诱导发光特性使得材料在薄膜状态下具有较高的荧光量子产率；从而将高效的激子利用和高效固态膜发光效率统一。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "目前，对于TADF材料的构筑策略，除了大家普遍借用的核心结构外，通常认为构筑分子密集的D-A基团组合及HOMO/LUMO轨道间的重叠是有效实现TADF性质的保证。而且大量的构效研究发现，存在分子内和分子间空间共轭的材料体系，也是一个TADF类材料普遍的结构特性。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.5　“热激子”材料" } ], "level": "2", "id": "s3e" } }, { "name": "p", "data": [ { "name": "text", "data": "最近，由我国科学家马於光院士倡导的“热激子”（Hot exciton）机制指导下的杂化局域-电荷转移态（Hybridized local and charge-transfer，HLCT）理论在构筑高效饱和深蓝光材料上展示了显著优势，并在多个材料体系及器件中得到了验证。与TADF不同，HLCT强调在分子激发态中布居高能级激子转化通道，并提出利用高能级CT态激子弱的束缚能来实现RISC过程，而在低能级的局域态（Locally excited，LE）辐射跃迁不受影响，从而实现激子辐射和激子转化的分离。由于热激子型材料中的辐射-跃迁过程对T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "激子的依赖程度较低，导致其器件制备过程并不需要掺杂来完成，减少了主客体能级匹配选择和共混的麻烦，降低了器件的成本，也可缓解T激子浓度猝灭导致的效率滚降问题，在OLED的稳定性和器件寿命方面具有潜在优势。另外，该类材料的主要辐射跃迁几乎由LE态为主的S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "态来完成，也很容易通过分子设计来实现对化合物光色和荧光效率的控制。" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "展示了部分“热激子”紫外/深蓝光材料。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "“热激子”紫外/深蓝材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "Molecular structures of “hot exciton” ultraviolet and deep-blue materials" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941974&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941977&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941975&type=", "width": "162.31298828", "height": "136.00518799", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "由于电致发光过程中激子的生成途径（载流子复合）与光致发光行为（电子跃迁）存在本质不同，导致激子动态过程与分子的能级及激发态的组成/分布存在密切关系。例如，通过在TADF的CT型T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "上添加能量接近的、LE态主导的T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "或T" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，则可以在显著增强S态和T态之间旋轨耦合作用（SOC）前提下，实现发光效率和稳定性的提升。这说明，调控发光分子中S态和T态中每个能级中LE/CT的组分及分布位置，可能是解决深蓝光效率和激子利用同步提升的有效方法。然而，由于发光分子多为一个共轭主体，每个基团化学结构或取代位置的改变通常都会导致材料性能的整体变化，往往是“顾此失彼”。尽管上述热激子过程主导HLCT理论在机制上已经打通了深蓝光材料的构筑之路；但是，在HLCT材料的能级调控上，还是形成了部分共识。由于材料的RISC过程发生在高的三线态T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "和单线态S" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "m" } ] } ] }, { "name": "text", "data": "之间（" }, { "name": "italic", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "≥2，" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "≥1），“热激子”材料从T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "向S" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "m" } ] } ] }, { "name": "text", "data": "的转化过程与从T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "向T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的内转换过程是竞争关系，实现“热激子”主导的电致发光过程需要材料具备大的T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "-T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级差以及小的T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "-S" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "m" } ] } ] }, { "name": "text", "data": "能隙，以加快T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "→S" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "m" } ] } ] }, { "name": "text", "data": "的窜越速率并抑制T" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "激子向更低振动能级的弛豫。事实上，大量的数据显示“热激子”材料在构筑蓝紫光材料方面是具有显著优势的：第一，高能级的RISC速率非常快，能有效避免三线态激子的积累和湮灭，表现为效率滚降小；第二，“热激子”材料无需引入强的D和A单元来实现前线轨道的分离，分子内较弱的电荷转移效应能够保证良好色纯度。以下将简单概述目前几类主要的热激子类蓝紫光材料的进展。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.5.1　基于菲并咪唑的HLCT材料" } ], "level": "3", "id": "s3e1" } }, { "name": "p", "data": [ { "name": "text", "data": "如上所述，菲并咪唑（PI）是非常具有潜力的深蓝光发光核心，而PI的苯基衍生物PPI虽呈现深蓝色发光，但其最大EQE仅有1.86%，这可能源于其较差的热稳定性。2014年，杨兵课题组设计合成了一系列激发态具有HLCT性质的发光材料，并通过溶剂化实验和量子化学计算验证了HLCT态特征" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "82", "type": "bibr", "rid": "R82", "data": [ { "name": "text", "data": "82" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于该系列材料的OLED光色从深蓝光至红光，其中，TPA-PA的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=418 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.0%的电致发光。紧接着，该课题组在PPI上引入间位三苯胺基团设计合成了近紫外发光材料mTPA-PPI" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。相比于PPI，三苯胺的引入使得mTPA-PPI的热稳定性有了显著提升，其" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "=120 ℃; 但间位引入三苯胺限制了分子的共轭长度，mTPA-PPI荧光量子产率降低。基于mTPA-PPI的OLED呈现深蓝光发射，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=404 nm，相应的CIE坐标为（0.16，0.05），色纯度高，光谱半峰全宽仅有47 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=3.33%，高亮度下的滚降非常小，可能存在“热激子”通道促进了mTPA-PPI电致发光过程中高能级三线态和单线态之间的RISC过程。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "深蓝光材料具有宽带隙，与红绿光材料相比，其载流子注入与传输更困难，常常通过构筑D-A结构解决该类问题。为避免ICT作用引起的光色红移，常选用弱的给受体基团构筑短波长发射材料，这可能会导致电致发光性能的其他方面失去原有优势。2015年，苏仕健课题组首次报道了基于强给体-受体基团的近紫外发光材料制备的OLED" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "83", "type": "bibr", "rid": "R83", "data": [ { "name": "text", "data": "83" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。采用间位连接的分子设计策略，阻断了联苯桥的共轭延伸，有效限制了给受体基团间强的分子内电荷转移，实现了对菲并咪唑异构体的分子内电荷转移作用有效调控。基于m-PTPAPI的OLED实现了近紫外发射，其电致发光峰在408 nm，相应的CIE坐标为（0.15，0.05），EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.39%。激子利用率超过25%归因于激发态具有HLCT态的特征，高能级的反系间窜越过程减缓了电致发光过程中三线态激子猝灭，基于m-PTPAPI的OLED均表现出平缓的效率滚降。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "为了避免强给受体之间的ICT作用引起的电致发光性能下降，2017年，李振声课题组报道了一种引入弱的n型间隔抑制ICT作用的分子设计策略，在菲并咪唑与三苯胺之间引入萘基团作为间隔基团，设计合成了一系列具有 HLCT特性的激发态分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "84", "type": "bibr", "rid": "R84", "data": [ { "name": "text", "data": "84" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，基于TPIBCz和TPIBNCz的OLED均实现了深蓝光发射，电致发光峰均在428 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为5.06%和6.03%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2020年，王悦课题组采用在菲并咪唑引入氟原子促进杂化激发态形成、提高激子利用率的策略，设计合成了三种强D-A结构的热激子材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "85", "type": "bibr", "rid": "R85", "data": [ { "name": "text", "data": "85" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，基于2FPPImTPA和2FPPIDPA的OLED均实现了深蓝光发射，其电致发光峰位分别为404 nm和420 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为4.10%和6.73%。氟取代不仅促进HLCT激发态的形成，氟原子之间的相互作用使得分子在固态下紧密堆积，2FPPImTPA和2FPPDTPA具有堪比商业传输材料的空穴传输能力。另一方面，紧密的堆积也使分子在聚集状态下产生了荧光猝灭现象，薄膜状态下荧光量子产率相对于溶液状态下大打折扣。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "平衡的空穴和电子传输能力有利于空穴与电子的均匀分布与充分复合，减少载流子在界面处的复合与聚集，提高了电致发光效率，同时能够简化器件结构。因此，设计具有双极传输的发光材料也成为实现高效电致发光的一个重要手段。2017年，王磊课题组设计合成了一系列含菲并咪唑与二苯基取代吖啶的深蓝光双极传输材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "86", "type": "bibr", "rid": "R86", "data": [ { "name": "text", "data": "86" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于DPACTPI、DPACFPPI、DPACPhTPI的OLED均实现了深蓝光发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为428，424，428 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为2.31%、3.03%、3.50%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2021年，冯新江等报道了一组具有杂化局域电荷转移态的双极性传输材料的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "87", "type": "bibr", "rid": "R87", "data": [ { "name": "text", "data": "87" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过苯桥对位连接菲并咪唑与咔唑/三苯胺，苯桥上引入三甲基硅增加空间位阻，设计合成了两种蓝紫光材料CSiTPI和DSiTPI。基于CSiTPI和DSiTPI的OLED的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别在404 nm和396 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别能达到7.1%和7.4%。具有双极传输能力、高三线态能级的短波长发射材料还可以用作其他发光材料的主体。分别以DSiTPI和CSiTPI作为主体制备了两种铱配合物的磷光器件，均实现了高效的磷光发射，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "在20.8%~23.0%之间且1 000 cd·m" }, { "name": "sup", "data": [ { "name": "text", "data": "-2" } ] }, { "name": "text", "data": "亮度下的效率滚降可忽略不计。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "四苯基硅具有宽带隙和高三线态能级的特点，能够有效打断共轭，其高度扭曲的正四面体结构使得材料具有较好的热稳定性。2021年，冯新江等设计合成了一种含双极芳基硅烷的D-π-A结构双极性紫光材料DSiPPI" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "88", "type": "bibr", "rid": "R88", "data": [ { "name": "text", "data": "88" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于DSiPPI的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=377 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=7.07%的电致发光。产生高效紫外发光最可能是源于高能态激子的反系间窜越，电致发光过程中部分三线态激子通过T" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "→S" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "通道转化为单态激子，从而实现了高效率和高激子利用率。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2022年，阎寿科课题组设计合成了两种菲并咪唑/三唑杂化的HLCT深蓝光材料，基于PITZF与PITZtCz的OLED均实现了深蓝光发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别在411 nm和413 nm， EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为7.21%和6.07%。其中，咔唑的引入在电子给体咔唑与电子受体三唑之间形成了一个强的CT作用，使得PITZtCz具有一个CT主导HLCT态，CT态的增强促进了hRISC的发生" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "89", "type": "bibr", "rid": "R89", "data": [ { "name": "text", "data": "89" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "综合分析目前已报道的数据，一般含有PI结构的蓝紫光材料多半都具有显著的HLCT特性，从而催生了人们对该结构材料体系的关注，认为其独特的构效关系可能是导致该性质的主要原因。例如，杨兵教授课题组从LE与CT杂化的角度在理论和实验上证明了其结构的特殊性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "90", "type": "bibr", "rid": "R90", "data": [ { "name": "text", "data": "90" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.5.2　基于咔唑的HLCT材料" } ], "level": "3", "id": "s3e2" } }, { "name": "p", "data": [ { "name": "text", "data": "咔唑作为一直被看好的深蓝光构筑基元，除了具有更饱和的蓝光发射外，高的三线态能级也是其被垂青的主要因素。另外，咔唑在9号位、3,6号位和2,7号位表现出相对较弱（与TPA比）且有差异的给电子性，特别有利于与弱受体结合，获得相对均衡的量子效率和光色。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2017年，杨文君课题组报道了一种咔唑-三唑杂化的近紫外发光材料PCZTZ" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "91", "type": "bibr", "rid": "R91", "data": [ { "name": "text", "data": "91" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。PCZTZ高度扭曲的分子骨架结构抑制了共轭长度的延伸，有效限制了聚集态下分子间的π-π相互作用。同时，PCZTZ分子间C—H…N键相互作用形成三维超分子氢键网络，显著提升了载流子传输性能。基于PCZTZ的OLED表现出了优异的电致发光性能，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=6.57%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=408 nm，相应的CIE坐标为（0.17，0.07）。优异的电致发光性能归因于PCZTZ良好的传输性能以及高荧光量子产率（PLQY=72%），最终实现了65.7%的激子利用率。PCZTZ的激发态具有HLCT态的特征，电致发光过程中能够通过高能级热激子通道实现对三线态激子的充分利用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2022年，赵祖金课题组报道了一系列具有HLCT特性的高效蓝紫光材料的电致发光性能，同时进一步拓展了蓝紫光材料的应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "92", "type": "bibr", "rid": "R92", "data": [ { "name": "text", "data": "92" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。POPCN-CP、POPCN-2CP、POPCN-2TBCP均具有高的固态荧光量子产率，其掺杂薄膜的荧光量子产率分别为83%、90%、88%，同时，快的高能级反系间窜越过程能够实现低滚降、高激子利用率的电致发光。基于POPCN-CP、POPCN-2CP、POPCN-2TBCP的OLED的" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为404，404，418 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为5.3%、8.2%、7.0%。为了充分发挥近紫外材料的主体潜力，以POPCN-2CP分子作为主体，分别制备了传统荧光、TADF和磷光等蓝光材料为发光客体的OLED。通过主客体间高效的能量传递，成功活化了FK306、FIrpic等商业化蓝光材料，实现了高效率、低滚降的蓝光OLED。宽带隙近紫外发光材料POPCN-2CP是非常具有潜力的主体材料，具有高三线态能级的紫外发光材料在做主体材料方向具有十分光明的前景。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "具有杂化局域电荷转移激发态性质的热激子材料能够实现快速的高能级的反系间窜越，具体表现为电致发光过程中的低效率滚降，这对于推动OLED的商业化发展有重要意义。高发光效率以及有限的共轭是高效蓝紫光的两个理想特征。一方面，构筑杂化激发态需要平衡好LE态和CT态的组分；另一方面，实现蓝紫光发射需要减少光色红移。因此，获得高效的蓝紫光热激子材料仍面临挑战。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.5.3　基于交叉长短轴策略的高效蓝紫光材料" } ], "level": "3", "id": "s3e3" } }, { "name": "p", "data": [ { "name": "text", "data": "除了典型的基元引入外，如何更好地建立HLCT分子构筑理论，一直是大家在不断总结的规律。随着对PIM构效关系的深入研究，在多个课题组及本课题组的研究基础上，我们逐步形成“交叉长短轴”（Crossed long-short axis，CLSA）的分子设计理念，并尝试其与局域激发态（LE）/电荷转移激发态（CT）的能级分布结合，逐步借助热激子和HLCT分子设计平台，发展利用LE态（S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）的高发光效率和高能级CT态RISC的高激子利用率的优势，制备出了系列高效率的OLED材料。例如，为了进一步提升器件效率，我们尝试在PIM的长轴方向引入具有聚集诱导发光特性的基团——四苯基乙烯来提高有机材料聚集状态下的光致荧光量子效率（PLQY）,在短轴方向引入苯氰基（A）来构筑CT态，并通过不同的连接方式（间位或对位）寻求分子激发态下LE和CT态的最优组分" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "93", "type": "bibr", "rid": "R93", "data": [ { "name": "text", "data": "93" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图 11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图 11" } ] } }, { "name": "text", "data": "（a）所示；然后，我们进一步精细调控LE和CT态分布位置，并通过理论化学模拟T→S势垒证明SOC可能是实现激子转化过程的又一重要参数，并通过掺杂和非掺杂的方式实现了目前最好的深蓝光发射器件，首次实现了高效率的敏化混和激发态主体-客体发光材料体系" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "94", "type": "bibr", "rid": "R94", "data": [ { "name": "text", "data": "94" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "（b）所示。同时，为了验证长短轴的可设计性和调控性，我们通过延展PIM中菲基共轭的形式来调整长短轴的取向，证明控制分子结构可以在PIM中实现LE和CT分布的有效调控，并首次采用静水压的方式实现了LE和CT态的逐步混合和切换" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "95", "type": "bibr", "rid": "R95", "data": [ { "name": "text", "data": "95" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "（c）所示。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "（a）激发态下LE和CT组分的调控" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "93", "type": "bibr", "rid": "R93", "data": [ { "name": "text", "data": "93" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；（b）平衡的LE/CT态分布有利于同时提高发光效率和激子利用率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "94", "type": "bibr", "rid": "R94", "data": [ { "name": "text", "data": "94" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；（c）静水压下LE和CT态的逐步混合和切换" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "95", "type": "bibr", "rid": "R95", "data": [ { "name": "text", "data": "95" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；（d）“交叉长短轴”概念图" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "96", "type": "bibr", "rid": "R96", "data": [ { "name": "text", "data": "96" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；（e）基于2Na-CzCN的OLED实现了高亮度下几乎可忽略不计的效率滚降" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "97", "type": "bibr", "rid": "R97", "data": [ { "name": "text", "data": "97" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；（f）高效近紫外光2MCz-CNMCz作为新型通用功能性主体材料的应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "98", "type": "bibr", "rid": "R98", "data": [ { "name": "text", "data": "98" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.11" } ], "title": [ { "name": "text", "data": "（a）Regulation of the proportion of LE and CT states in the excited state" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "93", "type": "bibr", "rid": "R93", "data": [ { "name": "text", "data": "93" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ".（b）The balanced LE/CT state distribution is beneficial to improve the efficiency and exciton utilization at the same time" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "94", "type": "bibr", "rid": "R94", "data": [ { "name": "text", "data": "94" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ".（c）Rehybridization and exchange of LE and CT states under pressure stimulation configuration" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "95", "type": "bibr", "rid": "R95", "data": [ { "name": "text", "data": "95" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ".（d）The concept map of “Crossed Long-short Axis”" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "96", "type": "bibr", "rid": "R96", "data": [ { "name": "text", "data": "96" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ".（e）The OLED based on 2Na-CzCN achieves almost negligible efficiency roll-off under high brightness" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "97", "type": "bibr", "rid": "R97", "data": [ { "name": "text", "data": "97" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ".（f）Application of high efficiency near ultraviolet material 2Na-CzCN as new-fashioned universal and functional host" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "98", "type": "bibr", "rid": "R98", "data": [ { "name": "text", "data": "98" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941979&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941983&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941981&type=", "width": "164.92108154", "height": "75.97874451", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为了证明该理论在材料设计中的普适性意义，我们以多个咔唑基团偶联的小扭曲角连接构筑分子长轴，N短轴引入吸电子基团苯氰基交错连接在分子长轴上，形成一个交叉耦合的D-A结构。其中，LE态主导的分子长轴延伸了共轭长度，有助于提高荧光量子产率；CT态主导的分子短轴一方面有利于载流子的注入，另一方面短轴高能级的电荷转移有助于加快RISC过程，实现高效的激子利用，借助二者正交构象达到平衡LE态和CT态的组分。2021年，我们课题组报道了一种高效紫外发光材料2BuCz-CNCz，基于2BuCz-CNCz的OLED具有目前为止紫外OLED领域报道的最高外量子效率，其EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=10.79%，" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=396 nm，相应的CIE坐标为（0.16，0.03），光谱半峰全宽仅有33 nm" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "96", "type": "bibr", "rid": "R96", "data": [ { "name": "text", "data": "96" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ", 如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "（d）所示。我们认为，优异的电致发光性能与“交叉长短轴”的分子设计策略有关，实现了高固态荧光量子产率（87.6%）以及电致发光过程中高激子利用率（51%~76%）。在电致发光过程中2BuCz-CNCz对三线态激子的捕获主要来源于T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/T" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "激子的高能级反系间窜跃过程，充分杂化的LE态和CT态使得2BuCz-CNCz分子具有较高的hRISC速率。2022年，我们在2BuCz-CNCz的基础上，引入中性的荧光生色团萘设计合成了效率滚降可忽略的紫外发光材料2Na-CzCN" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "97", "type": "bibr", "rid": "R97", "data": [ { "name": "text", "data": "97" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ", 如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "（e）所示。通过赋予长轴骨架更强的LE态特性，将光色进一步蓝移，实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=398 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=5.92%的高效、效率滚降可忽略的紫外电致发光。其中，以2Na-CzCN为主体，制备了橙光和红光磷光OLEDs，分别实现了25.3%和17.3%的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "，得益于2Na-CzCN 中T" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "→S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的hRISC过程，磷光器件在高电流密度下均表现出较低的效率滚降，这展示了紫外/近紫外材料作为磷光主体的潜力。同时，我们继续将长轴上的核心咔唑外围的修饰基团改变为3位偶联的咔唑调整LE态，并将短轴上苯氰基引入邻位甲基调控CT态，从而获得了性能优异的蓝紫光材料2MCz-CNMCz" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "98", "type": "bibr", "rid": "R98", "data": [ { "name": "text", "data": "98" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ", 如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "（f）所示。基于2MCz-CNMCz的OLED实现了" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=404 nm、EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=7.76%的电致发光，同时，2MCz-CNMCz作为多功能主体实现了对蓝色荧光、绿色、黄色和红色磷光材料的高效敏化。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2022年，卢华课题组报道了一种基于高空间位阻“风车型”结构模型的高效蓝紫光分子设计策略，借鉴了“CLSA”模型通过引入短轴平衡激发态中LE态和CT态的组分" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "99", "type": "bibr", "rid": "R99", "data": [ { "name": "text", "data": "99" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，高空阻“风车型”结构模型在保留LE态的基础上，引入更多的CT态，强化ICT效应，增大激子利用率，并兼顾通过增加空阻抑制ICT作用以及减少共轭长度的延伸。基于高空阻“风车型”结构模型，CTPPI分子的OLED实现了高效（EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=8.1%）和高激子利用率（88%~59%）的近紫外发光，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=403 nm，相应的CIE坐标为（0.16，0.04）；进一步以苯环代替对三联苯设计合成了CBPI分子，基于CBPI分子的OLED实现了深蓝光发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=428 nm，相应的CIE坐标为（0.15，0.06），EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=5.4%。 事实上，目前CLSA策略尽管在制备蓝紫光分子上获得了相对不错的结果，但作为基于实验总结归纳的分子设计新观点，仍有许多概念上的问题和理论瓶颈需要攻克。例如，为了能够更好地增加操作性而提出的在能级设计上发展的轴发光、挡板效应、插板效应等，在理论支持、数据分析和观点抽提尚有不完善之处，需要进一步丰满，从而实现高蓝光色纯度下最大比例的激子辐射（高荧光量子效率）和快速的激子RISC过程（高激子利用率）的统一。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.6　具有AIE特性的蓝紫光材料" } ], "level": "2", "id": "s3f" } }, { "name": "p", "data": [ { "name": "text", "data": "热活化延迟荧光与“热激子”是从捕获三线态激子的角度实现高效发光。具有聚集诱导发光或聚集增强发光特性的材料也能够实现高效发光，这类材料聚集态下具有较高的荧光量子产率，能够有效避免由分子密堆积导致的荧光猝灭。聚集诱导发光（Aggregation-induced emission，AIE）是由我国科学家唐本忠院士提出的概念，具有AIE性质的分子在溶液状态下不发光，在聚集状态下表现出强的荧光量子产率，这种独特的固态发光性质使得AIE材料在生物、OLED等领域中展现出了巨大应用潜力" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "100", "type": "bibr", "rid": "R100", "data": [ { "name": "text", "data": "100" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" }, { "name": "xref", "data": { "text": "图12", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12" } ] } }, { "name": "text", "data": "展示了具有聚集诱导增强发光或聚集增强发光特性的紫外/深蓝光荧光材料。" } ] }, { "name": "fig", "data": { "id": "F12", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图12" } ], "title": [ { "name": "text", "data": "具有AIEE或AEE特性的紫外/深蓝光荧光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 12" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue fluorescence materials with AIEE or AEE characteristics" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941985&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941989&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941987&type=", "width": "77.29284668", "height": "40.02758789", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2019年，王筱梅课题组报道了第一个具有聚集诱导增强发光（Aggregation-induced emission enhancement，AIEE）特性的紫外发光材料的电致发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "101", "type": "bibr", "rid": "R101", "data": [ { "name": "text", "data": "101" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Compd.3具有较显著的AIEE特性，聚集态的荧光量子产率相比于溶液状态提高，这归因于其具有分子内转动（Restriction of intramolecular rotation，RIR）性质的菲环核心。同时，Compd.3具有非常大的分子内二面角，扭曲的分子构象能够避免聚集状态下荧光猝灭。菲环的线性骨架有限的共轭长度能够实现短波长发射，基于Compd.3的OLED实现了紫外发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=383 nm，在420 nm处存在肩峰。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2020年，秦安军课题组报道了一系列具有聚集增强发光（Aggregation-enhanced emission，AEE）特性的紫外光材料的电致发光性能，在给受体结构中引入具有AIE特性基团——四苯基苯，设计合成了TPBCzC1、TPBCzC2、TPBCzC3三种聚集增强发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "102", "type": "bibr", "rid": "R102", "data": [ { "name": "text", "data": "102" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。得益于AEE特性，三种材料在薄膜状态下均具有超过98%的荧光量子产率。基于TPBCzC1与TPBCzC2的OLED实现了深蓝发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分别为422 nm和423 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "分别为4.34% 和4.78%，基于TPBCzC3的OLED实现了近紫外发射，其" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=405 nm，EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=2.76%。其中，基于TPBCzC1分子的OLED相应的CIE坐标为（0.16，0.04），首次实现了基于AIE发光材料的CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "<" }, { "name": "text", "data": "0.046的OLED。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在设计高激子利用率材料时引入具有AIE的功能团，可以获得兼具多种性能优势的发光材料，例如AIE-磷光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "103", "type": "bibr", "rid": "R103", "data": [ { "name": "text", "data": "103" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、AIE-HLCT材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "95", "type": "bibr", "rid": "R95", "data": [ { "name": "text", "data": "95" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": " 、AIDF" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "104", "type": "bibr", "rid": "R104", "data": [ { "name": "text", "data": "104" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "材料等。聚集诱导发光的发现是推动有机发光材料发展的关键一环，是推动OLED商业化进程的重要一步。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.7　含多重共振结构的蓝紫光材料" } ], "level": "2", "id": "s3g" } }, { "name": "p", "data": [ { "name": "text", "data": "作为OLED材料设计史上的又一次革命，多重共振策略打开了又一片天地。它与以往分子设计策略最大不同之处在于，利用给电子和吸电子原子之间的相反共振效应来实现光谱窄化以提高色纯度（半峰全宽低于30 nm），并非通过控制主峰位的单管策略；而且，由于电子共振被严格控制在原子层面，其辐射跃迁效率显著提高，因而材料的量子效率通常比较高。因此，MR型材料兼具了显示领域对于材料效率和光谱窄化的要求，成为学术界和工业界的新宠，在全光谱覆盖等方面高性能材料报道也如雨后春笋" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "105", "type": "bibr", "rid": "R105", "data": [ { "name": "text", "data": "105" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "106", "type": "bibr", "rid": "R106", "data": [ { "name": "text", "data": "106" } ] } } ], "rid": [ "R105", "R106" ], "text": "105-106", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，相关时效性综述较多，这里不再赘述。但是，由于这类材料几乎丧失了有机共轭体系的电子离域特性，因而开启电压都相对较高。但是，借助掺杂策略能提高其可应用性，而且也满足OLED材料设计中对于单一材料扮演单一角色的诉求，毕竟很多时候“多功能”的性质并不一定是好事。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在蓝紫光方面有代表性的MR型材料不多，这主要是大部分研究者认为，从实践需求的角度讲，这类材料的应用空间不大（不需要那么蓝）；但是作为科学理论探讨和潜在应用的拓展，蓝紫光MR材料也受到一些课题组的关注。" }, { "name": "xref", "data": { "text": "图13", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13" } ] } }, { "name": "text", "data": "展示了含有多重共振结构的深蓝光材料。2019年，Lee课题组合成了首例具有多重共振效应的近紫外材料tDIDCz" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "107", "type": "bibr", "rid": "R107", "data": [ { "name": "text", "data": "107" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于tDIDCz的OLED的电致发光峰位在401 nm，半峰全宽最小能达到14 nm，但是EQE较低，掺杂浓度3%时EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "仅有3.3%。" } ] }, { "name": "fig", "data": { "id": "F13", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图13" } ], "title": [ { "name": "text", "data": "含有多重共振结构的紫外/深蓝光材料" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 13" } ], "title": [ { "name": "text", "data": "Molecular structures of ultraviolet and deep-blue materials containing multiple resonance structures" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941990&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941992&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941991&type=", "width": "38.32562256", "height": "27.52236938", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图14", "type": "fig", "rid": "F14", "data": [ { "name": "text", "data": "图14" } ] } }, { "name": "text", "data": "依据关键的电致发光性能参数汇总了文中提到的紫外/深蓝光材料，目前发光峰位小于400 nm的紫外光材料与EQE超过10%的深蓝光材料相对较少，多数短波长发光材料集中在" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "=400~430 nm、EQE" }, { "name": "text", "data": "<" }, { "name": "text", "data": "6%的区域内。" } ] }, { "name": "fig", "data": { "id": "F14", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图14" } ], "title": [ { "name": "text", "data": "部分紫外/深蓝光材料的EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": "分布图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 14" } ], "title": [ { "name": "text", "data": "The EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": " and " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "EL" } ] }, { "name": "text", "data": " distribution map of a part of ultraviolet and deep-blue materials" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941995&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941998&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39941996&type=", "width": "72.21008301", "height": "44.57809448", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结　　论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "为了追求更好的蓝紫电致发光性能，不断提高OLED的电致发光性能，研究者们从电致发光峰位、发光效率、光致荧光量子产率、色纯度、器件结构、耐久性等方面提高材料的电致发光性能。为了进一步开拓紫外/深蓝光材料的应用，研究者们制备了以紫外/深蓝材料作为主体的磷光器件、基于紫外/深蓝材料的白光器件、以紫外/深蓝光材料作为空穴传输层的OLED器件，这些成功的尝试无一不为紫外/深蓝发光材料提供了新的应用方向。本文仅在有限的范围内归纳了近十年电致发光领域的紫外及深蓝光有机发光材料，旨在为从事该领域研究的工作者提供更多的数据参考。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "从科学研究和实际应用来看，优异的蓝紫光材料仍是推动OLED发展的关键之一，但如何实现真正的高效的器件，有太多因素需要调节和平衡。一方面，目前还不存在“十全十美”的发光机制，传统荧光材料和具有TTA特性的发光材料激子利用率受限，磷光材料和TADF材料受光色制约，HLCT材料的效率亟待新的突破，我们需要在已报道的材料体系中不断总结规律，形成一系列可参考的分子设计策略，从而快速地根据实际需要筛选合适的体系；另一方面，需要不断拓展新的基元结构，从而催生出更多的、更新的性质，在实现高性能时改变人们的认识和思维模式。目前，OLED作为已经进入规模化应用的领域，在材料和器件方面“内卷”都十分严重，对于研究单位和研究者在经费、硬件条件和知识积累等方面都提出了相当高的要求；要在激烈的竞争中寻求一席之地，唯有“创新”才能走出一条属于自己的道路。如何在纷繁的数据和文献中总结规律，站在巨人的肩膀上心沉气凝地审视已有成果，也是不断成长的关键。" } ] }, { "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": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } ], "href": 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