Using photoelectron spectroscopy, the interface formation of anatase and rutile TiO 2 with RuO 2 and tin-doped indium oxide (ITO) is studied. It is consistently found that the valence band maximum of rutile is 0.7 ± 0.1 eV above that of anatase. The alignment is confirmed by electronic structure calculations, which further show that the alignment is related to the splitting of the energy bands formed by the O 2p z lone-pair orbitals. The alignment can explain the different electron concentrations in doped anatase and rutile and the enhanced photocatalytic activity of mixed phase particles.SECTION: Surfaces, Interfaces, Porous Materials, and Catalysis A fter Fujishima and Honda 1 had reported on the photocatalytic activity of TiO 2 , the influence of crystal structure on this property was investigated intensively.2,3 Over the past 2 decades, it was commonly observed that mixed anatase/rutile systems show more favorable photocatalytic properties than pristine ones of either modification. 4−9 The synergistic effect of the mixed systems has been attributed to a built-in driving force for separation of photogenerated charge carriers. Such a driving force may result from either a built-in electric field or from energy barriers blocking charge transfer at the interface between anatase and rutile. The latter are described by the energy band alignment, which is well-studied for semiconductor interfaces. Connelly et al.11 recently reviewed several models that are trying to explain the synergistic effect of mixed anatase/rutile systems. Well-known are the rutile sink model of Bickley et al. 4 and the rutile antenna model of Hurum et al., 5 which place the band edges of rutile (energy band gap E g = 3.0 eV 12 ) in between the band edges of anatase (E g = 3.2 eV 13 ). Kavan et al.14 performed electrochemical measurements that located the conduction band edge of anatase 0.2 eV above that of rutile, which corresponds to aligned valence band maxima. These models, however, were not able to convincingly account for the observed synergistic phenomena. Only recently, Deaḱ et al. 15 as well as Scanlon et al. 16 found theoretical and experimental indications for an energy band alignment with valence and conduction band energies in rutile both located higher in energy than in anatase when brought into contact. With such a staggered energy band alignment at the anatase/rutile interface, photogenerated electrons will preferentially move to anatase due to its lower conduction band minimum energy E CB , and holes will move to rutile due to its higher valence band maximum energy E VB . Deaḱ et al. 15 used the alignment of branch point energies 10 for their calculations. For oxides, though, it has been shown that due to a low density of induced interface states, the alignment of branch point energies does not necessarily yield proper results for the energy band alignment. 17In this work, further evidence for a staggered energy band alignment at the anatase/rutile interface is provided by X-ray photoelectron spectroscopy (XPS)...

Nanoporous RuO 2 /TiO 2 heterostructures, in which ruthenium oxide acts as a quasi-metallic contact material enhancing charge separation under illumination, were prepared by impregnation of anatase TiO 2 nanoparticles in a ruthenium-(III) acetylacetonate solution followed by thermal annealing at 400 °C. Regardless of the RuO 2 amount (0.5−5 wt %), the asprepared nanocatalyst was made of a mesoporous network of aggregated 18 nm anatase TiO 2 nanocrystallites modified with RuO 2 according to N 2 sorption, TEM, and XRD analyses. Furthermore, a careful attention has been paid to determine the energy band alignment diagram by XPS and UPS in order to rationalize charge separation at the interface of RuO 2 /TiO 2 heterojunction. At first, a model experiment involving stepwise deposition of RuO 2 on the TiO 2 film and an in situ XPS measurement showed a shift of Ti 2p 3/2 core level spectra toward lower binding energy of 1.22 eV which was ascribed to upward band bending at the interface of RuO 2 /TiO 2 heterojunction. The band bending for the heterostructure RuO 2 /TiO 2 nanocomposites was then found to be 0.2 ± 0.05 eV. Photocatalytic decomposition of methylene blue (MB) in solution under UV light irradiation revealed that the 1 wt % RuO 2 /TiO 2 nanocatalyst led to twice higher activities than pure anatase TiO 2 and reference commercial TiO 2 P25 nanoparticles. This higher photocatalytic activity for the decomposition of organic dyes was related to the higher charge separation resulting from built-in potential developed at the interface of RuO 2 /TiO 2 heterojunction. Finally, these mesoporous RuO 2 −TiO 2 heterojunction nanocatalysts were stable and could be recycled several times without any appreciable change in degradation rate constant that opens new avenues toward potential industrial applications.

The energy band alignment at interfaces between different materials is a key factor, which determines the function of electronic devices. While the energy band alignment of conventional semiconductors is quite well understood, systematic experimental studies on oxides are still missing. This work presents an extensive study on the intrinsic energy band alignment of a wide range of functional oxides using photoelectron spectroscopy with in‐situ sample preparation. The studied materials have particular technological importance in diverse fields as solar cells, piezotronics, multiferroics, photo‐electrochemistry and oxide electronics. Particular efforts have been made to verify the validity of transitivity, in order to confirm the intrinsic nature of the obtained band alignment and to understand the underlying principles. Valence band offsets up to 1.6 eV are observed. The large variation of valence band maximum energy can be explained by the different orbital contributions to the density of states in the valence band. The framework provided by this work enables the general understanding and prediction of energy band alignment at oxide interfaces, and furthermore the tailoring of energy level matching for charge transfer in functional oxides. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

The doping of semiconductor materials is a fundamental part of modern technology, but the classical approaches have in many cases reached their limits both in regard to achievable charge carrier density as well as mobility. Modulation doping, a mechanism that exploits the energy band alignment at an interface between two materials to induce free charge carriers in one of them, is shown to circumvent the mobility restriction. Due to an alignment of doping limits by intrinsic defects, however, the carrier density limit cannot be lifted using this approach. Here, a novel doping strategy using defects in a wide bandgap material to dope the surface of a second semiconductor layer of dissimilar nature is presented. It is shown that by depositing an insulator on a semiconductor material, the conductivity of the layer stack can be increased by 7 orders of magnitude, without the necessity of high-temperature processes or epitaxial growth. This approach has the potential to circumvent limits to both carrier mobility and density, opening up new possibilities in semiconductor device fabrication, particularly for the emerging field of oxide thin film electronics.

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