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研究进展|深圳大学杨楚罗&曹啸松Angew:协同调控三重态密度和重原子效应实现半峰宽17nm的绿光发射

  • 2026-05-19 01:32:14
研究进展|深圳大学杨楚罗&曹啸松Angew:协同调控三重态密度和重原子效应实现半峰宽17nm的绿光发射

2026年4月27日Angewandte Chemie International Edition刊登了深圳大学杨楚罗教授、曹啸松教授等人关于TADF荧光材料调控的研究,文中报道了一种协同策略,将增加的三重态密度与适度的重原子效应相耦合,其中将一个能量匹配的含硫片段稠合到多共振热激活延迟荧光(MR‑TADF)骨架中,以加速反向系间窜越(RISC),同时保持窄带发射。《新能产学研》对本研究进行要点解读,供大家参考。

 研究背景 
在有机发光二极管(OLED)中,高效利用三线态激子是实现高外量子效率的关键。多共振热激活延迟荧光(MR‑TADF)材料兼具窄带发射和高光致发光量子产率,但其反向系间窜越速率(kRISC)通常较慢,导致效率滚降严重。本文通过在双硼MR骨架中引入含硫稠环单元(CzS),实现了三重态密度与适度重原子效应的协同调控。所获得的绿色发射体CzS‑BN在保持窄带发射(半峰宽17 nm)的同时,获得高达5.1×10⁶ s⁻¹的kRISC,基于其制备的非敏化器件实现了34.6%的最大外量子效率,在10000 cd m⁻²亮度下效率仍保持25.2%,色坐标达到(0.20, 0.74),接近BT.2020绿光标准。该工作首次在纯有机MR‑TADF体系中同时实现了超快RISC与超高清显示所需的色纯度。
 研究要点 

分子设计与合成

  • 构建了2×2分子库:DPS‑BN(非稠合含硫)、DPO‑BN(非稠合含氧)、CzO‑BN(稠合含氧)、CzS‑BN(稠合含硫)。CzS‑BN中稠合结构使二面角从25.5°减小至16.4°,骨架更刚硬。

  • 所有发射体热分解温度均高于500 °C,满足真空蒸镀要求。CzS‑BN的单晶结构确认了甲基的位阻导向作用,有效抑制了π‑π堆积。

理论计算与激发态特征

  • CzS‑BN在S₁附近存在多个热可达的三重态(ΔE<0.3 eV),且这些三重态具有互补的局域激发特征,增加了RISC通道密度。

  • 硫原子增强了不同电子特征态之间的自旋‑轨道耦合,而稠合结构将总重组能进一步降低50–75 cm⁻¹,有助于保持窄带发射。

光物理性质与激子动力学

  • 在甲苯溶液中,CzS‑BN发射峰为514 nm,半峰宽17 nm,CIEy达0.75。ΔEST为0.09 eV,与对照样品相近(0.09–0.10 eV),证明加速RISC并非源于ΔEST减小。

  • 在DMIC‑TRZ掺杂膜中,CzS‑BN的ΦPL高达98%,延迟荧光寿命仅2.4 µs,kRISC达5.1×10⁶ s⁻¹,分别是DPO‑BN、DPS‑BN、CzO‑BN的36.4倍、5.5倍和2.4倍,呈现显著的协同增强效应。

电致发光器件性能

  • 基于CzS‑BN的非敏化器件开启电压2.4 V,EL峰521 nm,半峰宽21 nm,CIE坐标(0.20, 0.74)。最大外量子效率、电流效率和功率效率分别为34.6%、133.5 cd A⁻¹和167.8 lm W⁻¹。

  • 在1000和10000 cd m⁻²亮度下,外量子效率仍保持32.1%和25.2%,远优于对照器件,归因于超快kRISC抑制了三线态‑三线态和三线态‑极化子湮灭。

 结论与展望 

本文提出并验证了通过同时增加三重态密度和引入适度重原子效应来加速MR‑TADF发射体RISC的协同策略。含硫稠环单元CzS的引入不仅提供了多个局域激发特征的热可达三重态,还增强了自旋‑轨道耦合,从而在不牺牲窄带发射的前提下实现超快三线态上转换。基于该策略的CzS‑BN在纯绿光OLED中实现了创纪录的效率与极低的效率滚降,其色坐标逼近BT.2020绿光标准。该设计思路可普适地应用于其他MR‑TADF骨架,为下一代超高清显示用高性能OLED材料提供了新方向。
文章地址:https://onlinelibrary.wiley.com/doi/10.1002/anie.4318204

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  1. CONNECT:[ UseTime:0.000584s ] mysql:host=127.0.0.1;port=3306;dbname=c460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000762s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000335s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000296s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000533s ]
  6. SELECT * FROM `set` [ RunTime:0.000257s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000624s ]
  8. SELECT * FROM `article` WHERE `id` = 569406 LIMIT 1 [ RunTime:0.000468s ]
  9. UPDATE `article` SET `lasttime` = 1779316604 WHERE `id` = 569406 [ RunTime:0.001931s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.002651s ]
  11. SELECT * FROM `article` WHERE `id` < 569406 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.002918s ]
  12. SELECT * FROM `article` WHERE `id` > 569406 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.003991s ]
  13. SELECT * FROM `article` WHERE `id` < 569406 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.008673s ]
  14. SELECT * FROM `article` WHERE `id` < 569406 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.002267s ]
  15. SELECT * FROM `article` WHERE `id` < 569406 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.001745s ]
0.097148s