Band lineup of layered semiconductor heterointerfaces prepared by van der Waals epitaxy: Charge transfer correction term for the electron affinity rule

The occurrence of quantum dipoles at layered materials semiconductor heterointerfaces was investigated by photoemission spectroscopy (PES). Due to the unique properties of layered compounds the prepared interfaces are essentially free of the structural problems known from the usually investigated heterosystems composed of III–V, IV or II–VI materials allowing the detailed investigation of electronic phenomena at the interfaces. We investigated heterostructures composed of epitaxial layers of SnS2 and SnSe2 on different single crystalline layered chalcogenide substrates (WSe2, MoS2, MoTe2, and GaSe). The epilayers were grown by van der Waals epitaxy (vdWe) on the (0001) plane of the substrate crystals. For every system the valence band offset was determined by careful evaluation of the PES data as a function of the film thickness. Using published values for the band gaps and the experimentally determined work functions and surface potentials the band lineup for each system was determined. The band offsets of all systems were found to differ from the prediction of the electron affinity rule (EAR) by a small systematic deviation which was related to the occurrence of localized quantum dipoles at the interface. This deviation can be expressed as a linear charge transfer correction term added to the original EAR. This corrected EAR is still a linear rule allowing the assignment of “characteristic energies” to each material for the calculation of the band offset. We could demonstrate that the error margin of the corrected EAR lies well within the experimental error of PES experiments, thus proving the general applicability of linear laws for the determination of the band offset in absence of structural dipoles.