Controlled electrical doping of organic semiconductors: a combined intra- and intermolecular perspective from first principles

The process of introducing extra charge carriers into organic semiconductors, or simply molecular doping, takes place via intermolecular charge transfer from the donor to the acceptor molecule. Using density functional theory calculations on diverse donor-acceptor pairs, we show that there are two modes of charge transfer; in one, charge transfer is controlled by the sign and in the other, by the magnitude of the donor HOMO-acceptor LUMO level offset. Despite doping being an intermolecular process, the identification of the transfer modes requires a full account of intramolecular geometric changes during charge transfer. We further show that the degree of charge transfer can be represented entirely by the reorganization energy, a common measure of geometric changes, of either the donor or the acceptor.