基于3, 6-二苯硒基咔唑的多重共振热活化延迟荧光分子

doi:10.6023/A25090323

研究论文

基于3, 6-二苯硒基咔唑的多重共振热活化延迟荧光分子

汪庆辉^†,a, 任正^†,a, 张凯^*,b, 周东营^*,a, 樊健^*,a,c

^a仿生界面材料科学全国重点实验室苏州大学功能纳米与软物质研究院苏州大学苏州 215123
^b物理与工程学院曲阜师范大学曲阜山东 273165
^c结构化学国家重点实验室福建福州 350002

投稿日期:2025-09-27
作者简介:†汪庆辉与任正为共同贡献者.
基金资助:
国家重点研发计划(No.2020YFA0714604,2024YFB3612102)和江苏省国际科技合作/港澳台科技合作项目(No.BZ2023053)资助.

Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3, 6- Diphenylselenylcarbazole

Wang Qinghui^†,a, Ren Zheng^†,a, Zhang Kai^*,b, Zhou Dongying^*,a, Fan, Jian^*,a,c

^aState Key Laboratory of Bioinspired Interfacial Materials Science, Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China
^bCollege of Physics and Engineering, Qufu Normal University, Qufu, Shandong, 273165, China
^cState Key Laboratory of Structural Chemistry, Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China

Received:2025-09-27
Contact: * E-mail: 15692312996@163.com; dyzhou@suda.edu.cn; jianfan@suda.edu.cn
Supported by:
National Key R&D Program of China (No. 2020YFA0714604, 2024YFB3612102), the International Science and Technology Innovation Cooperation/Hong Kong, Macao and Taiwan Science and Technology Innovation Cooperation Project of Jiangsu Province, China (No. BZ2023053).

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摘要/Abstract

传统的多重共振热活化延迟荧光材料(MR-TADF)的反向系间窜越速率(k_RISC)低, 器件在高亮度下效率滚降明显. 因此, 本工作利用硒的重原子效应, 增强S₁与T₁的自旋轨道耦合, 提高三线态激子反向系间窜越速率, 从而降低器件在高亮度下的效率滚降. 我们在经典的硼氮类多重共振热活化延迟荧光材料BCzBN的基础上, 设计并合成了一种将硒原子引入咔唑的3, 6号位上的分子即2SetCzBN. 2SetCzBN在稀甲苯溶液中的半峰宽为26 nm, ΔE_ST仅有0.14 eV, 并且分子具有大的自旋轨道耦合, 最终实现了高达2.49 × 10⁶ s^-1的反向系间窜越速率. 将2SetCzBN分子掺杂在主体材料9-(2-(9-苯基-9H-咔唑-3-基)苯基)-9H-3,9'-双咔唑(PhCzBCz)中制备的器件具有绿色发光, 当掺入15% (w) Firpic敏化时, 器件的最大外量子效率(EQE_max)可达到27.6%, 并且在1000 cd/m²的高亮度下, 器件的EQE 为22.2%, 具有很低的效率滚降; 通过调控电子传输层厚度为50 nm时器件最大EQE达到了31.3%.

关键词: 热激活延迟荧光, 重原子效应, 多重共振效应, 硒原子, 有机发光二极管

Conventional multiple resonance thermally activated delayed fluorescence material (MR-TADF) has a narrow emission spectrum with full width at half maximum (FWHM) <30 nm due to its planar rigid structure that suppresses vibrational relaxation and thus makes devices with higher color purity, but it usually faces the problem of a low rate of reverse intersystem crossing (k_RISC), and the device has a significant roll-off in efficiency at high luminance. Therefore, a molecule 2SetCzBN was designed and synthesized by introducing selenium atoms into the 3, 6 position of carbazole, which utilizes the heavy-atom effect of selenium to enhance the spin-orbit coupling effect of S₁ and T₁, accelerating the reverse intersystem crossing rate and thus decreasing the efficiency roll-off of the device at high luminance. The thermal decomposition temperature (temperature at 5% mass loss, T_d) of the compound 2SetCzBN was 388 ^°C, proving that it can be sufficient to withstand the heat treatment procedures during device preparation. The FWHM of 2SetCzBN in dilute toluene solution is 26 nm and the ΔE_ST is only 0.14 eV. The prompt fluorescence lifetimes of 2SetCzBN film is 1.3 ns and the delayed fluorescence lifetime is 3.27 μs. The orbital distribution and geometric configuration of 2setczbn are simulated, and the molecule has a high oscillator strength (f) of 0.4577. Meanwhile, the S₁ and T₁ of 2SetCzBN are hybrid local charge transfer (HLCT) excited states, and the T₂ energy level is mainly local excited states (LE). In addition, due to the influence of heavy atom effect, 2SetCzBN has a large spin-orbit coupling constant of 2.132 cm^-1, and finally achieves a high reverse intersystem crossing rate (2.49 × 10⁶ s^-1). Remarkably, when 2SetCzBN was doped in the host material PhCzBCz with 15% (w) Firpic as the sensitizer, the OLED device achieves a maximum EQE of 27.6%, and 22.2% at 10³ cd/m². Furthermore, the maximum EQE can reach 31.3% with the optimal thickness of the electron-transport layer (50 nm).

Key words: thermally activated delayed fluorescence, heavy atom effect, multiple resonance effect, selenium, organic light-emitting diode

引用此文

汪庆辉, 任正, 张凯, 周东营, 樊健. 基于3, 6-二苯硒基咔唑的多重共振热活化延迟荧光分子[J]. 化学学报, doi: 10.6023/A25090323.

Wang Qinghui, Ren Zheng, Zhang Kai, Zhou Dongying, Fan, Jian. Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3, 6- Diphenylselenylcarbazole[J]. Acta Chimica Sinica, doi: 10.6023/A25090323.

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参考文献

[1] Joo W. J.; Kyoung J.; Esfandyarpour M.; Lee S. H.; Koo H.; Song S.; Kwon Y. N.; Song S. H.; Bae J. C.; Jo A.; Kwon M. J.; Han S. H.; Kim S. H.; Hwang S.; Brongersma M. L.Science. 2020, 370, 459.
[2] Ge F.-J.; Zhang K.-Z.; Cao Q.-P.; Xu H.; Zhou T.; Zhang W.-H.; Ban X.-X.; Zhang X.-B.; Li N.; Zhu P. Acta Chim. Sinica 2023, 81, 1157(in Chinese). (葛凤洁, 张开志, 曹清鹏, 徐慧, 周涛, 张文浩, 班鑫鑫, 张晓波, 李娜, 化学学报, 2023, 81, 1157.)
[3] Hsiang E. L.; Yang Z. Y.; Yang Q.; Lan Y. F.; Wu S. T.J. Soc. Inf. Disp. 2021, 29, 446.
[4] Huang Y. G.; Hsiang E. L.; Deng M. Y.; Wu S. T. Light Sci. Appl. 2020, 9, 105.
[5] Liu P.-Y.; Tang Z.-F.; Sun W.-D.Journal of Jinan University, 2002, 23, 66(in Chinese). (刘彭义, 唐振方, 孙汪典, 暨南大学学报, 2002, 23, 66.)
[6] Mukherjee S.; Thilagar P.Chem. Commun. 2015, 51, 10988.
[7] Zhang Q. S.; Li J.; Shizu K.; Huang S. P.; Hirata S.; Miyazaki H.; Adachi C.J. Am. Chem. Soc. 2012, 134, 14706.
[8] Zheng X.; Yang C.-L.Chinese Journal of Luminescence 2022, 43, 1027(in Chinese). (郑贤, 杨朝龙, 发光学报, 2022, 43, 1027.)
[9] Uoyama H.; Goushi K.; Shizu K.; Nomura H.; Adachi C.Nature. 2012, 492, 234.
[10] Luo X. F.; Xiao X. W.; Zheng Y. X.Chem. Commun. 2024, 60, 1089.
[11] Ma J.-Z.; Li Y.; Gao S.; Zhao Y.; Ding L.; Zhou D.-Y.; Fan J.Acta Chim. Sinica 2025, 83, 17(in Chinese). (马金珠, 李阳, 高珊, 赵越, 丁磊, 周东营, 樊健, 化学学报, 2025, 83, 17.)
[12] Zhang D.-C.; Jia J.-H.; Liang D.; Cai X.-B.; Zhao Y.-Q.; Hu X.-L.; Jiang Y.-B.; Lu C.-Z. Acta Chim. Sinica 2024, 82, 887(in Chinese). (张登朝, 贾吉慧, 梁栋, 蔡显宝, 赵雨晴, 胡祥龙, 江钰冰, 卢灿忠, 化学学报, 2024, 82, 883.)
[13] Fang S.-Q.; Tong K.-N.; Chen S.-H.; Zhang Q.-F.; Tong B.-H.; Feng M.-Q.; Kong H. Acta Chim. Sinica 2025, 83, 471(in Chinese). (方素琴, 童恺宁, 陈思浛, 张千峰, 童碧海, 冯敏强, 孔辉, 化学学报, 2025, 83, 471.)
[14] Jiang H.; Jin J.-B.; Chen R.-F.; Zheng C.; Huang W.Prog Chem 2016, 28, 1811(in Chinese). (姜贺, 靳继彪, 陈润锋, 郑超, 黄维, 化学进展, 2016, 28, 1811.)
[15] Wang Y.-N.; Shao S.-Y.; Wang L.-X.Acta Chim. Sinica 2023, 81, 1202(in Chinese). (王一诺, 邵世洋, 王利祥, 化学学报, 2023, 81, 1202.)
[16] Hatakeyama T.; Shiren K.; Nakajima K.; Nomura S.; Nakatsuka S.; Kinoshita K.; Ni J.; Ono Y.; Ikuta T.Adv. Mater. 2016, 28, 2777.
[17] Yuan W. B.; Jin Q.; Du M. X.; Duan L.; Zhang Y. W.Adv. Mater. 2024, 36, 2410096.
[18] Meng G. Y.; Dai H. Y.; Wang Q.; Zhou J. P.; Fan T. J.; Zeng X.; Wang X.; Zhang Y. W.; Yang D. Z.; Ma D. G.; Zhang D. D.; Duan L.Nat. Commun. 2023, 14, 2394.
[19] Tankeleviciute E.; Samuel I. D.W.; Zysman-Colman, E.J. Phys. Chem. Lett. 2024, 15, 1034.
[20] Lin Y. J.;Jimenez-Garcia, K.; Spielman, I. B.Nature. 2011, 471, 83.
[21] Li R.; Wu Z.-M.; Li X.-F.; Wang X.-F.; Song Y.-Z.; Fan J.-Z.; Zhang G.-P.; Wang C.-K.; Lin L.-L.Chin. J. Chem. Phys. 2025, 38, 334.
[22] Park I. S.; Min H.; Yasuda T.Angew. Chem. Int. Ed. 2022, 61, e202205684.
[23] Li Q.; Wu Y. L.; Yang Q. Q.; Wang S. M.; Shao S. Y.; Wang L. X.ACS Appl. Mater. Interfaces. 2022, 14, 49995.
[24] Zhang Y. W.; Zhang D. D.; Wei J. B.; Liu Z. Y.; Lu Y.; Duan L.Angew. Chem. Int. Ed. 2019, 58, 16912.
[25] Hu Y. X.; Miao J. S.; Hua T.; Huang Z. Y.; Qi Y. Y.; Zou Y.; Qiu Y. T.; Xia H.; Liu H.; Cao X. S.; Yang C. L.Nat. Photonics. 2022, 16, 803.
[26] Hu Y. X.; Miao J. S.; Zhong C.; Zeng Y.; Gong S. L.; Cao X. S.; Zhou X.; Gu Y.; Yang C. L.Angew. Chem. Int. Ed. 2023, 62, e202302478.
[27] Xu Y. C.; Cheng Z.; Li Z. Q.; Liang B. Y.; Wang J. X.; Wei J. B.; Zhang Z. L.; Wang Y.Adv. Opt. Mater. 2020, 8, 1902142.
[28] Wang J. J.; Li N. Q.; Zhong C.; Miao J. S.; Huang Z. Y.; Yu M. X.; Hu Y. X.; Luo S.; Zou Y.; Li K.; Yang C. L.Adv. Mater. 2023, 35, 2208378.
[29] Zhang H.; Zhang B.; Zhang Y. W.; Xu Z.; Wu H. Z.; Yin P. A.; Wang Z. M.; Zhao Z. J.; Ma D. G.; Tang B. Z.Adv. Funct. Mater. 2020, 30, 2002323.
[30] Zhu T.-J.; Li L.-Y. Semiconductor Technology. 2007, 04, 358(in Chinese). (朱彤珺, 李来运, 半导体技术, 2007, 04, 358.)
[31] Ji X.-Q.; Li W.-Z.; Zhong Z.-Y.; Wang T.; Jiang Y.-D.Chinese Journal of Quantum Electronics. 2006, 23(3), 416(in Chinese). (季兴桥, 黎威志, 钟志有, 王涛, 蒋亚东, 量子电子学报, 2006, 23(3), 416.
[32] An R. Z.; Zhao F. M.; Shang C. J.; Zhou M.; Cui L. S.Angew. Chem. Int. Ed. 2025, 64, e202420489.
[33] Zhang Y. W.; Wei J. B.; Zhang D. D.; Yin C.; Li G. M.; Liu Z. Y.; Jia X. Q.; Qiao J.; Duan L.Angew. Chem. Int. Ed. 2022, 61, e202113206.
[34] Wang J.; Zhang F.-J.; Xu Z.; Wang Y.-S.Acta Phys. -Chim. Sin. 2012, 28, 949(in Chinese). (王健, 张福俊, 徐征, 王永生, 物理化学学报, 2012, 28, 949.)
[35] Wang Q.; Huang T.-Y.; Zhang D.-D.; Duan L.Chinese Journal of Luminescence 2023, 44, 77(in Chinese). (王琪, 黄天宇, 张东东, 段炼, 发光学报, 2023, 44, 77.)
[36] Chang C. H.; Lu Y. J.; Liu C. C.; Yeh Y. H.; Wu C. C.Journal of Display Technology. 2007, 3, 193.
[37] Yang X. L.; Zhou X. W.; Zhang Y. X.; Li, D. L; Li, C. S.; You C. F.; Chou T. C.; Su S. J.; Chou P. T.; Chi Y.Adv. Sci. 2022, 9, 2201150.
[38] Li W. J.; Lin T. Y.; Zhu F.; Yan D. H.J. Mater. Chem. C. 2025, 13, 16954.