ABSTRACT
An Al2O3/ZnO heterojunction was grown on a Si single crystal substrate by subsequent thermal and plasma-assisted atomic layer deposition (ALD) in situ. The band offsets of the heterointerface were then studied by consecutive removal of the layers by argon sputtering, followed by in situ X-ray photoelectron spectroscopy. The valence band maximum and conduction band minimum of Al2O3 are found to be 1.1 eV below and 2.3 eV above those of ZnO, resulting in a type-I staggered heterojunction. An apparent reduction of ZnO to elemental Zn in the interface region was detected in the Zn 2p core level and Zn L3MM Auger spectra. This suggests an interface formation different from previous models. The reduction of ZnO to Zn in the interface region accompanied by the creation of oxygen vacancies in ZnO results in an upward band bending at the interface. Therefore, this study suggests that interfacial properties such as the band bending as well as the valence and conduction band offsets should be in situ controllable to a certain extent by careful selection of the process parameters.
ABSTRACT
There is an urgent need for cheap, stable, and abundant catalyst materials for photoelectrochemical water splitting. Manganese oxide is an interesting candidate as an oxygen evolution reaction (OER) catalyst, but the minimum thickness above which MnOx thin films become OER-active has not yet been established. In this work, ultrathin (<10 nm) manganese oxide films are grown on silicon by atomic layer deposition to study the origin of OER activity under alkaline conditions. We found that MnOx films thinner than 1.5 nm are not OER-active. X-ray photoelectron spectroscopy shows that this is due to electrostatic catalyst-support interactions that prevent the electrochemical oxidation of the manganese ions close to the interface with the support, while in thicker films, MnIII and MnIV oxide layers appear as OER-active catalysts after oxidation and electrochemical treatment. From our investigations, it can be concluded that one MnIII,IV-O monolayer is sufficient to establish oxygen evolution under alkaline conditions. The results of this study provide important new design criteria for ultrathin manganese oxide oxygen evolution catalysts.
ABSTRACT
Cuprous oxide (Cu2O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu2O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu2O surface as well as the interface between Cu2O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu2O and provide guidance for future material development.
