Fractional and integer charge transfer at semiconductor/organic interfaces: The role of hybridization and metallicity

Inorganic/organic interfaces show two phenomenologically different types of charge transfer: On inert substrates, charge is localized, leading to a coexistence of neutral and charged molecules. Conversely, on metals, which have more available charge carriers and a larger propensity to hybridize, the charge is homogeneously delocalized. In this contribution, we use hybrid density functional theory to study the adsorption of the strong electron acceptor F4TCNQ on ZnO(10-10) as a function of the substrate's doping concentration. This system undergoes a joint charge donation/backdonation reaction. Because only the former is driven by hybridization, this allows us to study the impact of hybridization and the availability of charge carriers separately. We find that here both charge-transfer types are simultaneously at work. Whereas hybridization determines the charge localization, the charge-carrier concentration determines the amount of transferred charge. Consequently, at low doping concentrations, most of the electron acceptors become slightly positively, rather than negatively, charged.