Suppression of local electron-phonon interaction in pi-conjugated oligomers and its monitoring using Raman scattering

A.Yu. Sosorev
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Abstract

For efficient operation of many organic electronic devices, organic semiconductors with high charge carrier mobility are required. However, in most of the known organic semiconductors, the charge mobility is low, since it is limited by the strong local electron-phonon interaction. In the present work, using the example of thiophene-phenylene co-oligomers, a class of organic semiconductors that combine a sufficiently high charge mobility with light emission and therefore promising for light-emitting transistors and electrically pumped lasers, the mechanism of suppression of the electron-phonon interaction by introducing electronegative atoms or an additional thiophene ring is studied. It was found that such structural changes alter the contribution of various vibrational modes to the local electron-phonon interaction, in particular, to the suppression of the contribution of the low-frequency torsion mode. In addition, it is shown that for the two modes that make the largest contribution to the local electron-phonon interaction in an unsubstituted oligomer, this change correlates with their intensity of Raman scattering, and this confirms the promise of studying the electron-phonon interaction using Raman spectroscopy. The results obtained improve the understanding of the relationship between the local electron-phonon interaction and the molecular structure of organic semiconductors, which is extremely important for the directed design of such materials with high charge mobility.
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π共轭低聚物中局部电子-声子相互作用的抑制及其拉曼散射监测
为了使许多有机电子器件高效运行,需要具有高载流子迁移率的有机半导体。然而,在大多数已知的有机半导体中,电荷迁移率很低,因为它受到强烈的局部电子-声子相互作用的限制。在本工作中,以噻吩-苯基共低聚物为例,研究了通过引入电负性原子或额外的噻吩环来抑制电子-声子相互作用的机制。噻吩-苯基共低聚物是一类结合了足够高的电荷迁移率和光发射的有机半导体,因此有望用于发光晶体管和电泵浦激光器。研究发现,这种结构变化改变了各种振动模式对局域电子-声子相互作用的贡献,特别是对低频扭转模式贡献的抑制。此外,对于未取代低聚物中对局部电子-声子相互作用贡献最大的两种模式,这种变化与它们的拉曼散射强度相关,这证实了利用拉曼光谱研究电子-声子相互作用的前景。所得结果提高了对局域电子-声子相互作用与有机半导体分子结构之间关系的认识,这对定向设计高电荷迁移率材料具有重要意义。
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