V. Lashkaryov Institute of Semiconductor Physics NAS of Ukraine, pr. Nauki 41, Kyiv 03028, Ukraine.
Chem Rev. 2022 May 11;122(9):8487-8593. doi: 10.1021/acs.chemrev.1c00648. Epub 2022 Mar 17.
The exciton, an excited electron-hole pair bound by Coulomb attraction, plays a key role in photophysics of organic molecules and drives practically important phenomena such as photoinduced mechanical motions of a molecule, photochemical conversions, energy transfer, generation of free charge carriers, etc. Its behavior in extended π-conjugated molecules and disordered organic films is very different and very rich compared with exciton behavior in inorganic semiconductor crystals. Due to the high degree of variability of organic systems themselves, the exciton not only exerts changes on molecules that carry it but undergoes its own changes during all phases of its lifetime, that is, birth, conversion and transport, and decay. The goal of this review is to give a systematic and comprehensive view on exciton behavior in π-conjugated molecules and molecular assemblies at all phases of exciton evolution with emphasis on rates typical for this dynamic picture and various consequences of the above dynamics. To uncover the rich variety of exciton behavior, details of exciton formation, exciton transport, exciton energy conversion, direct and reverse intersystem crossing, and radiative and nonradiative decay are considered in different systems, where these processes lead to or are influenced by static and dynamic disorder, charge distribution symmetry breaking, photoinduced reactions, electron and proton transfer, structural rearrangements, exciton coupling with vibrations and intermediate particles, and exciton dissociation and annihilation as well.
激子是由库仑吸引力束缚的激发电子-空穴对,在有机分子的光物理中起着关键作用,并驱动着实际重要的现象,如分子的光诱导机械运动、光化学转化、能量转移、自由电荷载流子的产生等。与无机半导体晶体中的激子行为相比,它在扩展的π共轭分子和无序有机薄膜中的行为非常不同且非常丰富。由于有机体系本身的高度可变性,激子不仅对携带它的分子施加变化,而且在其整个寿命周期的所有阶段(即产生、转化和传输以及衰减)中都会发生自身变化。本综述的目的是系统而全面地介绍π共轭分子和分子组装体中激子的行为,重点关注这种动态图像中典型的速率以及上述动力学的各种后果。为了揭示激子行为的丰富多样性,考虑了不同体系中激子形成、激子输运、激子能量转换、直接和反向系间窜跃以及辐射和非辐射衰减的细节,其中这些过程导致或受到静态和动态无序、电荷分布对称性破缺、光诱导反应、电子和质子转移、结构重排、激子与振动和中间粒子的耦合以及激子解离和湮灭的影响。