Liao Jin-Long, Chen Xiwen, Liu Ching-Yang, Chen Show-An, Su Chiu-Huen, Su An-Chung
Department of Chemical Engineering, National Tsing-Hua University, Hsinchu, 30013 Taiwan, Republic of China.
J Phys Chem B. 2007 Sep 6;111(35):10379-85. doi: 10.1021/jp067878i. Epub 2007 Aug 15.
In molecular design of electroluminescent (EL) conjugated polymers, introducing a charge transport moiety on a side chain is found to be a promising method for balancing electron and hole fluxes in EL devices without changing the emitting color if there is no interaction between moiety and main chain. In the case of grafting a carbazole (Cz) moiety (hole transporting) on blue emitting polyfluorene, a green emission appears with intensity comparable to the blue emission, which was attributed to a possible interaction between main chain and Cz as previously reported by us. Here, a detailed study of its EL mechanism was carried out by means of time-resolved EL with the assistance of molecular simulation and thermally stimulated current measurements; exploration of how main chain segments interact with the transport moiety was performed. We found the Cz groups in Cz100PF play multiple roles: they act as (1) hole transporter to improve hole injection, (2) hole trapping site for efficient electron-hole recombination to yield blue-emitting excitons, and (3) source of green emission from electroplex formed via electric field-mediated interaction of the Cz/Cz radical cation with an electron in the nearby PF backbone. In combination, these observations suggest that integrated consideration for both intramolecular and intermolecular interactions provides a new route of molecular design of efficient EL polymers.
在电致发光(EL)共轭聚合物的分子设计中,如果侧链上引入的电荷传输部分与主链之间没有相互作用,那么这种方法被认为是在不改变发光颜色的情况下平衡EL器件中电子和空穴通量的一种很有前景的方法。在蓝色发光的聚芴上接枝咔唑(Cz)部分(空穴传输)的情况下,会出现强度与蓝色发射相当的绿色发射,正如我们之前报道的那样,这归因于主链与咔唑之间可能存在的相互作用。在此,借助分子模拟和热激电流测量,通过时间分辨电致发光对其电致发光机制进行了详细研究;探讨了主链段与传输部分之间的相互作用方式。我们发现Cz100PF中的咔唑基团发挥多种作用:它们充当(1)空穴传输体以改善空穴注入,(2)空穴俘获位点以实现高效的电子 - 空穴复合从而产生蓝色发射激子,以及(3)通过电场介导的咔唑/咔唑自由基阳离子与附近聚芴主链中的电子相互作用形成的电激复合物产生绿色发射的来源。综合起来,这些观察结果表明,对分子内和分子间相互作用的综合考虑为高效电致发光聚合物的分子设计提供了一条新途径。