基于热活化敏化荧光的蓝光材料与器件研究进展

王琪; 黄天宇; 张东东; 段炼

doi:10.37188/CJL.20220334

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基于热活化敏化荧光的蓝光材料与器件研究进展

特邀报告 | 更新时间：2023-02-16

- 基于热活化敏化荧光的蓝光材料与器件研究进展增强出版
- Research Progress of Blue Emission Materials and Devices Based on TADF Sensitized Fluorescence
- 发光学报 2023年 44卷第1期 (2023)
- 作者机构：
  
  清华大学化学系有机光电子与分子工程教育部重点实验室,北京,100084
- 作者简介：
- 基金信息：
  
  国家自然科学基金(51903137)
- DOI：10.37188/CJL.20220334 中图分类号： O482.31;TN312.8
- 纸质出版日期：2023-01-05，
  
  收稿日期：2022-09-15，
  
  修回日期：2022-10-07，
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引用本文
王琪,黄天宇,张东东等.基于热活化敏化荧光的蓝光材料与器件研究进展[J].发光学报,2023,44(01):77-89.

WANG Qi,HUANG Tianyu,ZHANG Dongdong,et al.Research Progress of Blue Emission Materials and Devices Based on TADF Sensitized Fluorescence[J].Chinese Journal of Luminescence,2023,44(01):77-89.
王琪,黄天宇,张东东等.基于热活化敏化荧光的蓝光材料与器件研究进展[J].发光学报,2023,44(01):77-89. DOI： 10.37188/CJL.20220334.

WANG Qi,HUANG Tianyu,ZHANG Dongdong,et al.Research Progress of Blue Emission Materials and Devices Based on TADF Sensitized Fluorescence[J].Chinese Journal of Luminescence,2023,44(01):77-89. DOI： 10.37188/CJL.20220334.

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In recent years， a new mechanism combining thermally activated delayed fluorescence （TADF） sensitizers and narrow spectrum final emitters， namely TADF sensitized fluorescence （TSF） has attracted more and more attention. With the continuous innovation of materials and device structures， performances of blue OLEDs based on this mechanism have been significantly improved. Here， focusing on the development of stable and efficient blue sensitizers， the progress in efficiency and lifetime of blue TSF devices in recent years is reviewed， and the future development goals and challenges are further discussed." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "有机发光二极管" } ], [ { "name": "text", "data": "热活化延迟荧光" } ], [ { "name": "text", "data": "热活化敏化荧光" } ], [ { "name": "text", "data": "高效稳定蓝光" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "organic light emitting diode" } ], [ { "name": "text", "data": "thermally activated delayed fluorescence" } ], [ { "name": "text", "data": "TADF sensitized fluorescence" } ], [ { "name": "text", "data": "efficient and stable blue OLED devices" } ] ] } ], "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": "有机发光二极管作为新一代显示技术，具有自发光、宽色域、广视角、对比度高、响应快等优点，被誉为21世纪“梦幻显示技术”。经过数十年发展，OLED技术趋于成熟并成功产业化，被广泛应用于手机、电脑、电视等各类显示器。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "OLED的研究核心在于开发高效稳定的材料和器件。第一代OLED" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } } ], "rid": [ "R1", "R2" ], "text": "1-2", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "基于传统荧光分子，具有稳定共价键、快速辐射跃迁速率（The rate of radiative decay, " }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "r" } ] }, { "name": "text", "data": "）、低三线态（T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）能量，在电致发光器件中稳定性较好。但由于无法利用电致激发产生的三线态激子，器件内量子效率（Internal quantum efficiency, IQE）受到限制（≤25%），使得第一代OLED器件效率偏低。第二代OLED材料解决了三线态激子利用问题。磷光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } } ], "rid": [ "R3", "R4" ], "text": "3-4", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "引入Os、Ir、Pt等重金属原子，利用重原子效应增大T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "与S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "之间的旋轨耦合常数（Spin-orbit coupling, SOC），使T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "激子辐射跃迁回到基态过程变为自旋部分允许。器件中电致激发产生的单线态（S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）激子系间窜越生成T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "激子随后辐射跃迁发光，实现了100%的激子利用率。但磷光分子中配位键相对较弱且T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "激子辐射跃迁缓慢，高亮度下三线态浓度显著升高，加剧了三线态-三线态湮灭（Triplet-triplet annihilation, TTA）及三线态-极化子湮灭（Triplet-polaron annihilation, TPA）等过程，进而损害器件稳定性" }, { "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": "。目前，绿色和红色磷光材料的效率及稳定性均已满足实际应用需求，但蓝色磷光材料由于激发态能量较高，稳定性仍然是瓶颈问题" }, { "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": "，OLED显示产品中只能使用低效的蓝色传统荧光材料。因此，开发兼具高效率与长寿命的蓝光材料成为OLED研究的“圣杯”" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "具有热活化延迟荧光特性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R8", "R9" ], "text": "8-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "的有机分子为解决上述问题提供了新思路。效率方面，TADF分子通过减小前线轨道重叠，降低单-三线态能量差（Δ" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{S T}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942296&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942292&type=", "width": "4.57200003", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）至0.2 eV以下，从而可利用环境热使T态激子向S态激子反向系间窜越" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "（Reverse intersystem crossing, RISC），由此实现100%的激子利用率。稳定性方面，TADF分子仅含有共价键，其键能大于磷光分子中的配位键；此外，TADF分子反向系间窜越速率（The rate of reverse intersystem crossing, " }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "）可以超过10" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": " s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，比磷光分子的辐射跃迁速率快一个数量级以上，能更快速利用三线态激子，有效抑制三线态激子湮灭过程，减少高能中间体的生成。经过十余年发展，目前基于TADF材料的天蓝光器件在1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的亮度下效率超过20%，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "97" } ] }, { "name": "text", "data": "（器件亮度衰减至初始亮度97%的时间）达到110 h" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，取得了令人瞩目的进展，展现了良好的产业化潜力。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "但是，TADF材料多为电子给体-电子受体型电荷转移态（Charge transfer, CT）分子，S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "辐射跃迁较慢且发射光谱宽，限制了稳定性与色纯度提升。为了克服上述矛盾，2012年，段炼等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "R12", "R13" ], "text": "12-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "提出了热活化敏化荧光机制，如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（a）所示。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "（a）TSF原理及激子能量传递路径；（b）蓝光光谱与CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "的关系。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "（a）Principle and exciton energy transfer path of TSF. （b）Relationship between spectrum and CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942281&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942289&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942285&type=", "width": "66.73315430", "height": "111.45078278", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "基于TSF机制的OLED器件选取TADF分子作为主体或敏化剂、窄光谱的硼氮分子或传统荧光分子为染料，利用TADF分子快速的反向系间窜越速率实现三线态激子上转换并通过Förster能量传递（Förster energy transfer, FRET）将激子能量转移给染料，最终利用染料辐射跃迁发光。 TSF机制由此实现发光层激子上转换与辐射跃迁的功能分解，结合了TADF分子快速上转换以及染料分子快速辐射跃迁优势，激发态寿命显著缩短，从而有利于提高器件寿命。TSF器件的另一个优势是可选择窄光谱荧光染料作为最终的发光材料。如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（b）所示，材料发射峰值相同，随着光谱半峰宽（Full width at half-maximum, FWHM）变窄，器件光色可由天蓝光蓝移至深蓝，TSF机制有望进一步提升器件寿命与色纯度" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "近年来，随着TADF敏化剂以及荧光染料的不断进步，基于TSF的蓝光器件效率和稳定性不断提升" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。本文围绕稳定蓝光TADF分子的设计开发综述了近年来该类型分子的研究进展以及TSF蓝光器件在寿命与效率方面取得的提升，并进一步指出未来发展的目标及面临的挑战。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　高效稳定蓝光TADF分子开发" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "TADF分子在TSF器件中具有激子上转换功能，是实现三线态激子高效利用的关键，需要兼具较好的本征稳定性与快速的反向系间窜越速率。稳定性方面，由于蓝光对应激发态能量较高，仅含有较稳定C—H、C—C、C—N化学键的氰基、1,3,5-三嗪、9H-咔唑等刚性基团及其衍生物被遴选出来，作为电子受体、电子给体应用于蓝光敏化剂分子的构筑，衍生出三嗪-咔唑、苯腈-咔唑两大体系。激子利用方面，由于蓝光染料辐射跃迁速率普遍可以超过1×10" }, { "name": "sup", "data": [ { "name": "text", "data": "8 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，远大于TADF分子反向系间窜越速率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，上转换过程成为发光层激子利用的决速步。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "加速激子利用、抑制三线态激子湮灭对提升器件稳定性至关重要。如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "所示，在纯有机TADF分子中，三线态激子上转换至单线态受自旋禁阻限制为动力学缓慢过程，其寿命达到微秒量级。高亮度下长寿命三线态激子浓度上升，通过短程Dexter能量传递（Dexter energy transfer, DET）发生三线态-三线态湮灭、三线态-极化子湮灭等过程产生高能中间态，进而使材料化学键裂解、器件老化。因此研究者一方面引入惰性位阻基团屏蔽发光核心，减小相邻分子间前线轨道重叠抑制DET；另一方面则增大TADF分子反向系间窜越速率，加快三线态激子上转换动力学过程，降低三线态激子浓度，从根本上抑制激子湮灭过程，进而降低效率滚降（Roll-off），提高器件稳定性。但是，电子给体-受体型TADF分子在光色蓝移与提高反向系间窜越速率之间存在矛盾：光色蓝移要求降低给受体的给电子与吸电子能力，并需要一定程度上减小给受体平面之间的扭转角抑制分子内电荷转移；高效上转换过程要求保持较强的分子内电荷转移，增大TADF分子前线轨道分离程度保证较小的Δ" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{S T}

k_{R I S C} = \frac{2 π}{ћ} ρ_{F C} {\"\"\"|\"\"<\"\" separators=\"|\">, S_{1} | {\hat{H}}_{S O C} | T_{1}\"\"\"\"|\"}^{2},

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942316&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942315&type=", "width": "44.61933517", "height": "7.87400007", "fontsize": "" } } }, { "name": "text", "data": " " } ], "id": "DF1" } }, { "name": "p", "data": [ { "name": "text", "data": "其中，|" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

\hat{H}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942322&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942319&type=", "width": "2.70933342", "height": "3.64066648", "fontsize": "" } } } ] }, { "name": "sub", "data": [ { "name": "text", "data": "SOC" } ] }, { "name": "text", "data": "|为S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "与T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间的SOC矩阵元；" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

ρ_{F C}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942327&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942325&type=", "width": "4.48733330", "height": "4.48733330", "fontsize": "" } } } ] }, { "name": "text", "data": "为弗兰克-康登加权态密度（Franck-condon-weighted density），该项化简后正比于" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

e x p (- Δ E

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942335&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942329&type=", "width": "13.46199989", "height": "3.64066648", "fontsize": "" } } } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

/ k

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942341&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942339&type=", "width": "2.70933342", "height": "2.70933342", "fontsize": "" } } } ] }, { "name": "sub", "data": [ { "name": "text", "data": "B" } ] }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

T)

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942352&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942346&type=", "width": "3.89466691", "height": "3.47133350", "fontsize": "" } } } ] }, { "name": "text", "data": "，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "表示单线态-三线态能量差，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "B" } ] }, { "name": "text", "data": "为玻尔兹曼常数。因此，相关分子设计策略围绕减小Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "、增大SOC展开。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2011年，Endo等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "在" }, { "name": "italic", "data": [ { "name": "text", "data": "Appl. Phys. Lett." } ] }, { "name": "text", "data": " 发表了第一个应用于OLED的TADF材料PIC-TRZ。但该类型分子电子给体强度较大，难以实现光色蓝移，后续蓝光分子多以2,4,6-三苯基-1,3,5-三嗪为电子受体，电子给体键连在苯环上。" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "中结构式a所示的蓝光TADF分子Cz-TRZ掺杂在DPEPO薄膜中，S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级高达3.18 eV，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "接近0.4 eV，器件最大外量子效率仅为4.5%。因此后续工作主要集中于在9H-咔唑的3,6位置连入取代基团（结构通式b）、对1,3,5-三嗪与9H-咔唑间桥连基团进行修饰（结构通式c）以及引入多给体（结构通式d），从而适当地使光色红移并降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "，提高器件效率与稳定性。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "开发高效稳定三嗪-咔唑体系蓝光TADF分子策略" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "Development strategy of efficient and stable blue emission TADF molecules for Triazine-Carbazole system" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942358&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942366&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942362&type=", "width": "76.07876587", "height": "73.26095581", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2014年，Hirata等" }, { "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": "以9H-咔唑、3,6-二苯基-9H-咔唑为取代基，设计合成了2c（" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "= 9H-咔唑, " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "= H）、2b（" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "= " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "= 9H-咔唑）、2a（" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "= " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "= 3,6-二苯基-9H-咔唑）一系列蓝光TADF分子。如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "所示，电子给体π共轭体系的延展导致了HOMO的离域化，增强了电子振动耦合并降低了前线轨道重叠程度，从而减小Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "，加快反向系间窜越过程。由于取代基接入2a等分子相较于Cz-TRZ光色稍有红移，2b、2c甲苯溶液中发射峰为458 nm，2a为457 nm，但Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "显著减小，其中2a仅为0.09 eV。以2a为染料、DPEPO为主体的器件取得了最优性能，器件色坐标CIE为（0.19, 0.35），为天蓝光发射，最大外量子效率超过20%，1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下外量子效率仍接近11%，展现出较小的效率滚降。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "2a/2b/2c结构式与前线轨道分布" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "Chemical structure of 2a/2b/2c and their frontier orbital distribution" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942371&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942377&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942375&type=", "width": "77.67480469", "height": "77.25585938", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2015年，Kim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": "利用相同的策略分别在苯环上以间位连接的方式接入2个/4个9H-咔唑基团，设计了两个稳定蓝光TADF分子DCzTrz、DDCzTrz，通过促进HOMO离域化降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "。两个分子Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "相近，约为0.25 eV，相较于Cz-TRZ大幅度降低。以DPEPO为主体，DCzTrz、DDCzTrz为染料的器件最大外量子效率分别为17.8%、18.9%，色坐标CIE分别为（0.15, 0.16）、（0.16, 0.22）。为提升器件稳定性，研究者进一步选用" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP为主体，DCzTrz、DDCzTrz为染料，对比器件以光色相近的磷光分子为染料，发光层为" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP∶Ir（dbi）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "。500 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下，DDCzTrz器件" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "80" } ] }, { "name": "text", "data": "达到52 h，是对比器件的3倍，展现出三嗪-咔唑体系TADF分子良好的稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2017年，崔林松等" }, { "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": "以甲基为位阻基团，设计合成了一系列具有TADF性质的深蓝光分子，如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（a）所示，其中" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=Me, " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=H记为Cz-TRZ1；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=Me，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=H记为Cz-TRZ2；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "CZ-TRZ1~4的结构式（a）与优化构型（b）" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "Chemical structures（a）， optimized geometries（b） for molecules Cz-TRZ1-4." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942381&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942387&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942384&type=", "width": "161.25428772", "height": "55.69924927", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "Me，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=H记为Cz-TRZ3；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=Me，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=H记为Cz-TRZ4。在9H-咔唑1,8位置引入甲基一定程度上增强了电子给体能力，Cz-TRZ3甲苯溶液中发射峰红移至465 nm，而桥连基团修饰对光色影响较小，Cz-TRZ1、Cz-TRZ3、Cz-TRZ4甲苯溶液发射峰基本相同。位阻基团的引入增大了给受体平面的扭转角，其中Cz-TRZ1二面角仅为49.8°，而Cz-TRZ2、Cz-TRZ3、Cz-TRZ4分别为86.7°、71.3°、82.3°。分子构型扭曲化促进HOMO-LUMO分离，降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "，加快反向系间窜越速率。未经修饰的为Cz-TRZ1为0.43 eV，相近光色的Cz-TRZ3、Cz-TRZ4分别为0.17 eV、0.15eV，反向系间窜越速率达到1.53×10" }, { "name": "sup", "data": [ { "name": "text", "data": "4 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "与2.83×10" }, { "name": "sup", "data": [ { "name": "text", "data": "4 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，是Cz-TRZ1的51倍与94倍。以Cz-TRZ3为染料、DPEPO为主体的器件取得了最优性能，器件最大外量子效率为19.2%，色坐标CIE为（0.148, 0.098），接近标准深蓝光发射。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "但是，甲基化学活性较强不利于分子电化学稳定性，作为替代，更稳定且具有刚性结构的苯环被引入以调控分子的发光性质。2021年，Jeon等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "选用苯环作为位阻基团设计合成了一系列TADF分子，其中" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=Ph," }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=H记为PPCzTrz；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=Ph，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "=H记为PCzTrz。苯环的引入同样增大了给受体平面扭转角从而提高了分子TADF性质，PPCzTrz分子Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "为0.16 eV，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "达到8.02×10" }, { "name": "sup", "data": [ { "name": "text", "data": "4 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "；作为对比，PCzTrz分子Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "为0.23 eV，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "仅为1.44×10" }, { "name": "sup", "data": [ { "name": "text", "data": "4 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。值得一提的是，该项工作以PPCzTrz、PCzTrz为敏化剂，" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "-DABNA为染料制备了OLED器件，发光机制以及能量转移路径如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "所示。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "Jeon等工作的光物理特性（a）与发光机制（b），插图为敏化剂PPCzTrz的结构式。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "Photophysical characteristics（a） and emission mechanisms（b） of Jeon " }, { "name": "italic", "data": [ { "name": "text", "data": "et al" } ] }, { "name": "text", "data": ".’s work. Inset shows the chemical structure of the sensitizer PPCzTrz." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942390&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942396&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942393&type=", "width": "77.99047852", "height": "61.93750000", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "上述器件中主体三线态能量低于TADF敏化剂三线态能量、高于染料三线态能量。主体承担激子传输与复合功能，TADF敏化剂完成三线态激子上转换过程与三线态激子分配，部分三线态激子能量传递给主体再传递给染料，染料兼顾发光并辅助激子上转换，由此保障器件高效率的同时降低主体三线态激子能量，提高器件稳定性。该机制激子利用关键步骤为TADF敏化剂承担的三线态激子上转换过程。以PPCzTrz为TADF敏化剂、" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "-DABNA为染料制备的器件性能最优，最大外量子效率超过33%，色坐标CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "=0.17，1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "约3 h，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "超过150 h。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "El-Sayed规则指出" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } } ], "rid": [ "R23", "R24" ], "text": "23-24", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，为保持总角动量守恒，具有相同构型特征的S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间的ISC和RISC是自旋禁阻的。因此，若TADF分子S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "构型均为电荷转移态（分别为" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT和" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT），即使降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "提高仍有限，这是大多数D-A型TADF分子" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "难以突破10" }, { "name": "sup", "data": [ { "name": "text", "data": "6 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "的原因。为解决这个问题，研究者在桥连基团上连入多重给体，一方面使HOMO离域化，减小Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "同时增强态混合，增大S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "与T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间的SOC；另一方面构建能级接近简并的激发态，增加三线态激子上转换通道。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2020年，崔林松等" }, { "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": "利用该策略设计合成了一系列分子。当" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "通式d中Ds均为9H-咔唑时，记为5Cz-TRZ。该分子Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "仅为0.06 eV，兼具LE与CT态的T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "使得SOC" }, { "name": "sub", "data": [ { "name": "text", "data": "S1-T1" } ] }, { "name": "text", "data": "达到0.4 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，相较于常规TADF分子提升超过4倍。如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "所示，T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "-T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "间能量差低至0.24 eV，SOC" }, { "name": "sub", "data": [ { "name": "text", "data": "S1-T2" } ] }, { "name": "text", "data": "则超过1 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，使得T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "-S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "成为三线态激子反向系间窜越的有效通道。叠加以上因素，该分子" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "达到1.5×10" }, { "name": "sup", "data": [ { "name": "text", "data": "7 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。以5Cz-TRZ为染料、" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP为主体构建的验证器件，实现了486 nm的天蓝光发射，器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=29.3%，5 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下EQE=27%，效率滚降低于10%；寿命方面，高效快速的三线态激子上转换抑制了TTA、TPA等过程，1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下器件" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "90" } ] }, { "name": "text", "data": "接近600 h。另外，研究者以5Cz-TRZ为敏化剂、传统荧光分子TBPe为染料制备了天蓝光器件，得益于敏化剂快速上转换速率，器件最大外量子效率超过20%且效率滚降较小。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "多通道反向系间窜越能级示意图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "Schematic diagram of multi-channel reverse inter system crossing" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942398&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942403&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942400&type=", "width": "70.61201477", "height": "49.61466980", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　苯腈‑咔唑体系" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "文献中最早报道的苯腈-咔唑类蓝光TADF分子为2CzPN" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，该分子在器件中发射峰约470 nm，最大外量子效率未超过10%。由于苯二腈作为电子受体过强，难以实现光色蓝移，单苯腈-咔唑成为该体系中高效蓝光代表性分子。由于" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "结构式a所示分子2CzBN-1" }, { "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": "甲苯稀溶液发射峰过蓝，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "高达0.31 eV，且氮气氛围下PLQY仅有13%，后续优化工作主要集中于引入多重给体（结构通式b）、引入第二给体（结构通式c）、氰基对位键连受体（结构通式d），从而使光色适当红移、降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "提升反向系间窜越速率、抑制非辐射跃迁提升PLQY等。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "开发高效稳定苯腈-咔唑体系蓝光TADF分子策略" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "Development strategy of efficient and stable blue emission TADF molecules for Benzonitrile-Carbazole system" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942406&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942414&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942410&type=", "width": "77.93652344", "height": "71.39169312", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2016年，段炼课题组" }, { "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": "率先报道了单苯腈咔唑类蓝光材料，并引入多重给体，获得了一系列从天蓝光到深蓝光TADF分子，" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "通式b中" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "= 9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=H记为4CzBN；" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=3,6-二叔丁基-9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=叔丁基，" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=H记为4TCzBN；" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=H记为5CzBN；" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "=3,6-二叔丁基-9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=叔丁基记为5TCzBN（5TCzBN）。如" }, { "name": "xref", "data": { "text": "图 9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图 9" } ] } }, { "name": "text", "data": "（a）所示，由于线性D-π-D结构有助于形成Cz" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "自由基，该自由基与BN" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "相互作用形成离域激发态并增强" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE电子振动耦合，因此可以增大分子反向系间窜越速率" }, { "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": "。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "（a）5CzBN分子中离域CT态和线性D-π-D结构形成示意图；（b）5CzBN衍生物的分子结构及能级图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "（a）Schematic illustration of the formation of delocalized CT states and the linearly positioned donors in the 5CzBN molecule. （b）Molecular structure of 5CzBN derivatives along with the energy diagrams." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942416&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942421&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942418&type=", "width": "73.36480713", "height": "109.98785400", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "另外，基于B3LYP杂化密度泛函的计算表明，存在多个中间三线态陈列于整体分子S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "-T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间，这些中间三线态可能对激子上转换有一定帮助。以5CzBN为例，如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "（b）所示，源自m-3CzBN和4CzBN的中间三重态位于整体分子5CzBN的S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "-T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间，可能是5CzBN具有较大反向系间窜越速率的因素之一。2019年，Adachi 团队" }, { "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": "通过瞬态吸收证实了中间三线态的存在，它们来自于具有多重给受体分子的部分分子结构，为理论计算提供了实验证据。结合以上因素，4CzBN、4TCzBN、5CzBN、5TCzBN反向系间窜越速率均有一定提升，其中5CzBN达到1.13×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，5TCzBN达到1.81×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，且由于多重给体导致分子结构拥挤刚性增强，抑制了非辐射跃迁，5CzBN、5TCzBN分子的PLQY均超过70%。值得注意的是，位阻基团叔丁基的引入屏蔽发光核心，进一步抑制了三线态激子湮灭。如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（a）所示，5TCzBN分子HOMO分布被严格限制在咔唑上，并未分布到咔唑的3,6位取代基，这意味着叔丁基作为惰性位阻基团，不仅增大了分子间距离，也减小了相邻分子前线轨道重叠，对抑制三线态激子湮灭过程起到重要作用。以5CzBN、5TCzBN为染料，" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP为主体制备的验证器件光色上两者色坐标几乎一致（CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "≈0.40），都呈现天蓝光发射；效率上5TCzBN器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=21.2%，为5CzBN器件的1.26倍，证明引入叔丁基减少了电致激发下三线态激子的损失；而器件寿命对比更为明显（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": " （b）），5TCzBN器件500 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "达到770 h，是5CzBN器件的5倍。这是首个高效率、长寿命TADF天蓝光材料，该策略也被广泛应用于后续TADF分子设计。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "5CzBN及5TCzBN的化学结构及HOMO分布（a）、器件寿命对比（b）。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "Comparison of chemical structure and HOMO distribution（a） and device lifetime（b） of 5CzBN and 5TCzBN." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942425&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942430&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942428&type=", "width": "64.58660889", "height": "100.15979004", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "虽然D-π-D结构帮助增强了" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE电子振动耦合，但受限于" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT间较大的能量差，氰基咔唑体系进一步增大反向系间窜越速率仍有困难" }, { "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": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2018年，Noda等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "尝试引入具有较低" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE能级的第二给体。如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "所示，以5CzBN为原型分子，分别引入3,6-二甲基-9H-咔唑（meCz）和3,6-二苯基-9H-咔唑（DPhCz）作为第二给体设计合成了一系列蓝光TADF材料，" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "结构通式c中" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "= 3,6-二甲基-9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=H记为3Cz2DMeCzBN；" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=3,6-二苯基-9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=H记为3Cz2DPhCzBN；" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=3,6-二苯基-9H-咔唑," }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=Ph记为2Cz3DPhCzBN。通过调整第二给体的数目和给电子能力，" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE态能级得到有效调节，显著降低了" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE-" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT能量差。与5CzBN相比，所有具有第二受体的分子均显示出PLQY的增加和TADF性质的改善。其中，3Cz2DPhCzBN分子" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE-" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT能量差为0.16 eV，相较5CzBN降低了0.16 eV，在Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "几乎没有变化的情况下该分子甲苯溶液中反向系间窜越速率达到7.2×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，超过5CZBN的6倍。以3Cz2DPh‑ CzBN为染料的蓝色OLED器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=20.9%，色坐标CIE为（0.21, 0.44），呈天蓝光发射，初始亮度1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "97" } ] }, { "name": "text", "data": "=110 h。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "（a）3Cz2DPhCzBN及2Cz3DPhCzBN分子结构式；（b）" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "、" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级排列示意图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.11" } ], "title": [ { "name": "text", "data": "（a）Chemical structure of 3Cz2DPhCzBN and 2Cz3⁃DPhCzBN. （b）Schematic illustration of " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "， " }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "， and " }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": " energy level alignment for RISC." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942433&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942437&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942435&type=", "width": "80.01995850", "height": "67.85498047", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2021年，Chan等" }, { "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": "利用相同的策略设计合成了天蓝光敏化剂HDT-1，分子结构为" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "结构通式c中" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "=3,6-二苯基-9H-咔唑，" }, { "name": "italic", "data": [ { "name": "text", "data": "D" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "=间三联苯，" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=H。该分子掺杂在" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP薄膜中呈485 nm天蓝光发射，PLQY为86%，反向系间窜越速率达到9.2×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": " s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。以HDT-1为染料、" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "CBP为主体的器件最大外量子效率为22%，CIE为（0.19, 0.40），初始亮度1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "=28 h。为进一步提高器件色纯度，以HDT-1为敏化剂、" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "-DABNA为染料构建了TSF器件。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图12", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12" } ] } }, { "name": "text", "data": "展示了典型的TSF器件能级排布与激子能量传递路径。实现“天蓝光敏化深蓝光”的原因有两点：一是具有CT性质的敏化剂激发态能量分布广泛；二是" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "-DABNA分子小的斯托克斯位移使染料吸收光谱与敏化剂发射光谱间有较大重叠，建立了高效的FRET。较好的材料搭配降低了体系激发态能量,结合敏化剂、染料良好的本征稳定性与快速激子利用速率，验证器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "≈27%、CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "=0.20、1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "=11 h。" } ] }, { "name": "fig", "data": { "id": "F12", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图12" } ], "title": [ { "name": "text", "data": "Chan等工作的光物理特性（a）与发光机制（b），插图为敏化剂HDT-1的结构式。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.12" } ], "title": [ { "name": "text", "data": "Photophysical characteristics（a） and emission me⁃chanisms（b） of Chan " }, { "name": "italic", "data": [ { "name": "text", "data": "et al" } ] }, { "name": "text", "data": ".'s work. Inset shows the chemical structure of the sensitizer HDT-1." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942439&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942443&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942441&type=", "width": "77.99047852", "height": "61.93750000", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "然而，多重给体带来的问题在于光色过度红移，上转换速率较快的分子几乎都红移至天蓝光发射，色纯度较差。如何保持高反向系间窜越速率的同时使光色蓝移仍存在挑战。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "降低" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT间能量差的另一个策略为弱化电子给体强度，提升" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT能量。2020年，段炼课题组" }, { "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": "提出使用苯腈代替氰基，弱化给体使光色蓝移的同时，抬升" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT、" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT能量。由于" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE能量不受电子受体强弱影响，因此同样起到了减小" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE-" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT能量差的作用。如" }, { "name": "xref", "data": { "text": "图13", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13" } ] } }, { "name": "text", "data": "所示，p4TCzPhBN的" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT能级与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE能级相同，均为2.98 eV，而" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT也提升至2.88 eV，两者间能量差仅为0.1 eV。另外，p4TCzPhBN同样具有线性D-π-D、A- π-A结构，电致激发下形成的Cz" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "自由基与BN" }, { "name": "sup", "data": [ { "name": "text", "data": "- " } ] }, { "name": "text", "data": "相互作用形成离域激发态，增强" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE电子振动耦合，对增大" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "亦有帮助。此外，值得注意的是，多重给受体引入使得p4TCzPhBN激发态能量接近简并状态，计算显示p4TCzPhBN分子具有较小Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "的同时，T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "、T" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "能量位于S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "-T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "之间，T" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "-S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "、T" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "-S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "可能成为辅助三线态激子反向系间窜越的有效通道。" } ] }, { "name": "fig", "data": { "id": "F13", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图13" } ], "title": [ { "name": "text", "data": "（a）CzBNs和CzPhBNs的相对能级图；（b）p4TCzPhBN化学结构与该分子" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "、" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级排列示意图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.13" } ], "title": [ { "name": "text", "data": "（a）The relatively energy level diagram of CzBNs and CzPhBNs. （b）Chemical structure of p4TCzPhBN and the energy levels of p4TCzPhBN obtained from the spectra measured in toluene." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942446&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942453&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942450&type=", "width": "121.49291992", "height": "88.12464905", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "综合以上因素，p4TCzPhBN分子" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "超过2.3×10" }, { "name": "sup", "data": [ { "name": "text", "data": "6 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，发射峰在甲苯稀溶液中蓝移至456 nm。以该分子为染料、DPEPO为主体制备的验证器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=22.8%，CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "<" }, { "name": "text", "data": "0.2，在1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下EQE仍超过20%，展现出极小的效率滚降。为进一步提升色纯度，以mCPCz为主体、p4TCzPhBN为敏化剂、" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "text", "data": "-DABNA为染料构建了TSF器件，最大外量子效率为32.5%，色坐标CIE为（0.13, 0.12），100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下器件" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "80" } ] }, { "name": "text", "data": "超过3 000 h。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "另外，多重给体导致分子量偏大，且分子构型拥挤，整体呈球形，一定程度上影响了光取出率。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2022年，段炼课题组" }, { "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": "提出延展受体π共轭体系策略，设计合成了一系列深蓝光TADF分子，" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "结构通式d中" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=Ph，A为苯环记为2PCzBN-Ph；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=Ph，A为对叔丁基苯记为2PCzBN-tPh；" }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "=Ph，A为对氟苯记为2PCzBN-FPh。该策略通过减少咔唑受体数量增强分子平面性，提升了材料发光偶极水平取向，同时在氰基对位引入吸电子基团扩大受体共轭，增大LUMO离域程度，提升了材料TADF性质。LUMO离域化一方面使前线轨道重叠减小，从而降低Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ST" } ] }, { "name": "text", "data": "，另一方面增强了" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT与" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE电子振动耦合，如" }, { "name": "xref", "data": { "text": "图14", "type": "fig", "rid": "F14", "data": [ { "name": "text", "data": "图14" } ] } }, { "name": "text", "data": "所示。据此设计的2PCzBN-FPh反向系间窜越速率达到8.31×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，超过多重给体型分子5CzBN的7倍，且甲苯溶液中光色蓝移至454 nm，分子水平取向达到84%，PLQY超过90%。" } ] }, { "name": "fig", "data": { "id": "F14", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图14" } ], "title": [ { "name": "text", "data": "2PCzBN衍生物的前线轨道分布与计算能级排布（a）、化学结构（b）。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.14" } ], "title": [ { "name": "text", "data": "The calculated distributions of their frontier molecular orbitals as well as the energy levels（a）， and the structures（b） of the 2PCzBN derivatives." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942455&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942458&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942457&type=", "width": "116.39697266", "height": "94.07539368", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "以2PCzBN-FPh为染料掺杂在主体PPF中构建的验证器件EQE" }, { "name": "sub", "data": [ { "name": "text", "data": "max" } ] }, { "name": "text", "data": "=35.7%，CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "=0.25， 1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "下器件EQE≈25%，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": "超过100 h，展现出较小的效率滚降与较好的器件寿命，为氰基/咔唑体系开发提供了新的范例，实现了性能突破。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.3　其他稳定蓝光TADF分子" } ], "level": "2", "id": "s2c" } }, { "name": "p", "data": [ { "name": "text", "data": "传统D-A结构的TADF材料给体与受体之间的共轭效应会产生能量低的分子轨道，光色显著红移，不利于蓝光材料开发。空间扭曲的D-A结构" }, { "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": "以及非共轭的σ桥连的D-σ-A结构" }, { "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": "是抑制共轭保持蓝光的常用策略。然而，上述结构均难以兼顾蓝光材料效率和稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2022年，张东东等" }, { "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": "提出了D-Void-A的抑制D/A共轭效应新策略：由于分子轨道的形成需要给体和受体各自轨道电子云的空间重叠，而理论计算表明占吨酮3号碳原子上没有HOMO以及HOMO-1轨道的分布，给体基团与C3键连时能有效抑制给体-受体间HOMO共轭，转而与能级更深的受体HOMO-2形成分子轨道从而拉大发光带隙（" }, { "name": "xref", "data": { "text": "图15", "type": "fig", "rid": "F15", "data": [ { "name": "text", "data": "图15" } ] } }, { "name": "text", "data": "）。相较于引入σ键打断共轭，D-Void-A结构的分子具有一定的HOMO-LUMO重叠，振子强度更大且具有较强的分子骨架刚性，有效抑制了非辐射跃迁。基于该策略设计的33PCX光色蓝移至440 nm，PLQY达到92%，反向系间窜越速率为4.3×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": " s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。以33PCX为染料、PPF为主体的器件最大外量子效率为27.5%，CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "=0.252。为进一步提升器件色纯度，以33PCX为敏化剂、" }, { "name": "italic", "data": [ { "name": "text", "data": "v" } ] }, { "name": "text", "data": "-DABNA为染料构建了敏化器件，色坐标CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "=0.19，100 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "初始亮度下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "超过650 h，证实了占吨酮单元作为TADF分子受体的良好稳定性，为后续工作提供了新的分子设计思路。" } ] }, { "name": "fig", "data": { "id": "F15", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图15" } ], "title": [ { "name": "text", "data": "D-void-A结构示意图及占吨酮-咔唑敏化剂分子" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.15" } ], "title": [ { "name": "text", "data": "Structure diagram of D-void-A and xanthone-carbazole sensitizers" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942461&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942465&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942463&type=", "width": "67.36358643", "height": "117.00006104", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　总结与展望" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "围绕蓝光敏化剂分子开发和TSF器件优化两个核心课题，研究人员为构建高效稳定蓝光OLED器件付出了诸多努力，在多个子课题上取得突破。提高材料本征稳定性方面，利用重水将TADF分子中C—H键氘代为C—D键，抑制因化学键振动造成的非辐射跃迁并浅化激发态势能面，提高PLQY同时抑制分子处于高能激发态时的化学键裂解，从而提高敏化剂的稳定性" }, { "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": "；高效敏化剂开发方面，通过增强态混合、减小" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "CT-" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CT-" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "LE能量差、构筑多重通道三线态激子上转换、开发新给受体" }, { "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": "、引入空间电荷转移" }, { "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": "等策略，打破TADF分子光色蓝移与提高上转换速率之间的制约，深蓝光TADF敏化剂" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "RISC" } ] }, { "name": "text", "data": "达到甚至超过10" }, { "name": "sup", "data": [ { "name": "text", "data": "6 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，有效降低高电流密度下三线态激子浓度，抑制了激子湮灭过程；窄光谱染料设计方面，于稠环芳烃结构中引入硼（B）、氮（N）、氧（O）等多种或单一杂原子，降低前线轨道在化学键上的分布来抑制键长变化导致的振动耦合与构型弛豫，开发了新型高发光效率、窄光谱多重共振（Multiple resonance, MR）分子，提高了器件色纯度；抑制发光层激子损失方面，引入刚性大位阻基团屏蔽发光核心，减小相邻分子间前线轨道重叠，抑制Dexter能量传递，减少发光及能量传递过程中的激子损失；器件优化设计方面，合理设计发光层材料搭配优化器件能级排布，避免激子直接被染料捕获、降低体系激子能量，提高器件效率的同时延长器件寿命。目前基于氘代敏化剂的深蓝光TSF器件CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "~0.19，1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "80" } ] }, { "name": "text", "data": "超过450 h，外量子效率达到16%，由于叠层器件、顶发光设计等器件工程能进一步优化发光色纯度、提高器件效率、延长器件寿命" }, { "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": "，全氘代器件结合器件工程将助力蓝光TSF OLED向产业化目标迈出一大步。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "当然，TSF OLED产业化仍面临巨大挑战。为了满足高分辨率4K/8K显示器的广色域标准，蓝光OLED色坐标要求降低至（0.131, 0.046），这需要在目前工作的基础上进一步蓝移，开发发射峰小于470 nm、反向系间窜越速率大于10" }, { "name": "sup", "data": [ { "name": "text", "data": "6 " } ] }, { "name": "text", "data": "s" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "的稳定敏化剂，光谱半峰宽小于18 nm、发射峰在460 nm左右的高效发光染料，以及与之适配的宽带隙双极性主体。从与现有工艺的匹配而言，二元而非三元TSF系统值得进一步研究。二元TSF系统主体兼具激子传输、复合与敏化功能，从而简化器件制备工艺、减少发光层激子能量传递造成的能量损失，降低器件工作电压。另外，作为竞争机制，近年来蓝色磷光OLED器件与磷光辅助的热活化敏化荧光（Phosphor-assisted TADF-sensitized fluorescence, TPSF）器件发展迅速，目前效能最好的蓝色磷光OLED器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "~0.2，在1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下外量子效率超过23%，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "达到150 h；效能最好的蓝色TPSF器件" }, { "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": "CIE" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "text", "data": "~0.17，在1 000 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "亮度下外量子效率近26%，" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "95" } ] }, { "name": "text", "data": "达到73 h，成为蓝光TSF OLED产业化的重要竞争对手。不过，TSF OLED在材料成本、元素丰度等方面具有磷光材料无法比拟的优势，为蓝色磷光OLED以及TPSF器件开发的稳定的主体及传输层材料亦可提高TSF OLED的性能。相信三者之间的竞争将促进高效、稳定的蓝光OLED产业化。" } ] }, { "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": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } } ] }, { "name": "p", "data": [ { "name": "text", "data": "CJL.20220334." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "TANG C W" }, { "name": "text", "data": "， " }, { "name": "text", "data": "VANSLYKE S A" }, { "name": "text", "data": ". 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