Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body Theory

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 (C6F6) and BF3 are also investigated as dopants for 4T. Modeling the adducts as bimolecules 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:BF3, 4T:C6F6). In the optical spectrum of 4T:BCF, a charge-transfer excitation appears at the lowest energy, corresponding to the transition between the frontier states, which exhibit very small but nonvanishing 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.