论文标题
从\ textit {ab intib}多体理论的微观洞察力洞察BCF掺杂的寡头碘的电子结构
Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from \textit{Ab initio} Many-Body Theory
论文作者
论文摘要
刘易斯酸（如Tris（五氟苯基）硼烷（BCF））提供了有机$ P $有机半导体的有前途的路线。到目前为止，有趣的实验结果呼吁更深入地了解潜在的掺杂机制。在第一个原理的工作中，基于最先进的密度功能性理论和多体扰动理论，我们研究了由BCF掺杂的四分之一思奇（4T）形成的供体/受体复合物的电子和光学特性。作为参考，还研究了Hexafluorobenzene（C $ _6 $ F $ _6 $）和BF $ _3 $作为4T的掺杂剂。将加合物建模为bimolecules \ textit {in Vacuo}，我们发现在接地状态和边界轨道上的电荷转移可以忽略不计，要么在界面的相对侧（4T：BCF）隔离，要么定位于供体（4T：4T：4T：BF $ _3 $，4T：C $ _6 $ _6 $ f $ _6 $ _6 $ _6 $ _6 $ _6 $ _6 $）。在4T：BCF的光谱中，电荷转移激发出现在最低能量，对应于边境状态之间的过渡，后者表现出很小但不变的波函数重叠。在其他两个加合物中，吸收是由成分特征的叠加给出的。我们的结果阐明了供体和受体之间的内在电子相互作用对BCF和相关路易斯酸引起的掺杂机制概不负责。为此，必须系统地分析外部因素，例如溶剂 - 溶质相互作用，分子间耦合和热力学效应。
Lewis acids like tris(pentafluorophenyl)borane (BCF) offer promising routes for efficient $p$-doping of organic semiconductors. The intriguing experimental results achieved so far call for a deeper understanding of the underlying doping mechanisms. In a first-principles work, based on state-of-the-art density-functional theory and many-body perturbation theory, we investigate the electronic and optical properties of donor/acceptor complexes formed by quarterthiophene (4T) doped by BCF. For reference, hexafluorobenzene (C$_6$F$_6$) and BF$_3$ are also investigated as dopants for 4T. Modelling the adducts as bimolecules \textit{in vacuo}, we find negligible charge transfer in the ground state and frontier orbitals either segregated on opposite sides of the interface (4T:BCF) or localized on the donor (4T:BF$_3$, 4T:C$_6$F$_6$). In the optical spectrum of 4T:BCF, a charge-transfer excitation appears at lowest-energy, corresponding to the transition between the frontier states, which exhibit very small but non-vanishing wave-function overlap. In the other two adducts, the absorption is given by a superposition of the features of the constituents. Our results clarify that the intrinsic electronic interactions between donor and acceptor are not responsible for the doping mechanisms induced by BCF and related Lewis acids. Extrinsic factors, such as solvent-solute interactions, intermolecular couplings, and thermodynamic effects, have to be systematically analyzed for this purpose.
