The dependence of hydrogen coverage on the bulk doping concentration is investigated for the polar O-terminated (0001̅ ) ZnO surface. We use hybrid density-functional theory in combination with ab initio thermodynamics to determine a doping-dependent phase diagram of this surface. For hydrogen coverages lower than 50% dangling oxygen bonds remain at the surface, where they subsequently become charged by bulk electrons. For such charged surfaces, a computational firstprinciples approach is presented, with which long-range band bending can now be included in firstprinciples supercell calculations. In this work, we use a modified and extended version of the recently introduced charge-reservoir electrostatic sheet technique (Sinai et al 2015 Phys. Rev. B 91 075311) to incorporate band bending effects directly into our first-principles calculations. This allows us to investigate the effect of space charge layers and the resulting band bending on the hydrogen coverage of the ZnO (0001̅ ) surface. After introducing a new implementation of CREST, we show that the structure and stability of polar ZnO surfaces are indeed sensitive to the amount of free charge carriers in the bulk. At low doping concentrations our results corroborate the previously reported (2 × 1) hydrogen phase, at higher doping concentrations the hydrogen coverage diminishes notably.

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.

Charge transfer at organic/inorganic interfaces critically influences the properties of molecular adlayers. Although for metals such charge transfers are well documented by experimental and theoretical results, in the case of semiconductors, clear and direct evidence for a transfer of electrons or holes from oxides with their typically high ionization energy is missing. Here, we present data from infrared reflection–absorption spectroscopy demonstrating that despite a high ionization energy, electrons are transferred from ZnO into a prototype strong molecular electron acceptor, hexafluoro-tetracyano-naphthoquinodimethane (F6-TCNNQ). Because there are no previous studies of this type, the interpretation of the pronounced vibrational red shifts observed in the experiment was aided by a thorough theoretical analysis using density functional theory. The calculations reveal that two mechanisms govern the pronounced vibrational band shifts of the adsorbed molecules: electron transfer into unoccupied molecular levels of the organic acceptor and also the bonding between the surface Zn atoms and the peripheral cyano groups. These combined experimental data and the theoretical analysis provide the so-far missing evidence of interfacial electron transfer from high ionization energy inorganic semiconductors to molecular acceptors and indicates that n-doping of ZnO plays a crucial role.

The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.