Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from \textit{Ab initio} Many-Body Theory

TL;DR

This study uses advanced first-principles calculations to analyze how BCF and similar Lewis acids interact electronically with oligothiophenes, revealing that intrinsic electronic interactions are not the main doping mechanism, highlighting the need to consider extrinsic factors.

Contribution

It provides a detailed ab initio analysis of BCF-doped oligothiophenes, showing that doping mechanisms are not driven by intrinsic electronic interactions but likely involve extrinsic effects.

Findings

Negligible charge transfer in ground state complexes

Charge-transfer excitation observed in BCF-doped oligothiophenes

Intrinsic interactions are not responsible for doping mechanisms

Abstract

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.