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The properties of a sol-gel prepared Mn-modified TiO2 film have been studied with X-ray absorption spectroscopy (XAS) and photoelectron spectroscopy (PES) using synchrotron radiation. The chemical composition and oxidation state of the elements have been determined. The manganese content estimated by PES of the Mn-modified film is about 10% and both Mn2+ and Mn3+ are observed. Addition of Mn is found to modify the valence band edge. The Mn 3d states are found to extend about 1 eV into the TiO 2 band gap region. It is demonstrated that lithium insertion into the sol-gel film can be performed in a stepwise fashion in situ under ultrahigh vacuum (UHV) conditions. Lithium is distributed evenly throughout the entire film and leads to reduction of Mn3+ to Mn2+ followed by reduction of Ti4+ to Ti3+. The XAS and PES measurements give fully consistent results regarding the amount of inserted lithium.

We present measurements of the Zr and Si core level photoelectron binding energies relative to the Fermi level and the vacuum level under a ZrO2 growth series on Si(100). It is shown that the Zr core level binding energy is most properly referenced to the local vacuum level already from the monolayer regime. This confirms the insulating properties of ZrO2. The Si core levels are referenced to the Fermi level and undergo shifts consistent with the disappearance of the mid-band-gap states originating from the (2×1) reconstruction on the clean Si(100) surface. The use of O 1s x-ray absorption spectroscopy (XAS) to determine the location of the conduction band edge of ZrO2 is discussed with the aid of ab initio calculations. It is demonstrated that the conduction band edge is located at the XAS peak position and that the position relative to the valence band can be determined by aligning the O 1s XAS spectrum to the O 1s photoelectron spectrum. The study thus establishes that photoelectron spectroscopy in conjunction with x-ray absorption spectroscopy forms a most powerful tool for studies of the band alignment at metal oxide-silicon interfaces.

The growth of ultrathin ZrO2 films on Si(1 0 0)-(2 × 1) and Si(1 1 1)-(7 × 7) has been studied with core level photoelectron spectroscopy and X-ray absorption spectroscopy. The films were deposited sequentially by chemical vapor deposition in ultra-high vacuum using zirconium tetra-tert-butoxide as precursor. Deposition of a > 50 Å thick film leads in both cases to tetragonal ZrO2 (t-ZrO2), whereas significant differences are found for thinner films. On Si(1 1 1)-(7 × 7) the local structure of t-ZrO2 is not observed until a film thickness of 51 Å is reached. On Si(1 0 0)-(2 × 1) the local geometric structure of t-ZrO2 is formed already at a film thickness of 11 Å. The higher tendency for the formation of t-ZrO2 on Si(1 0 0) is discussed in terms of Zr–O valence electron matching to the number of dangling bonds per surface Si atom. The Zr–O hybridization within the ZrO2 unit depends furthermore on the chemical composition of the surrounding. The precursor t-butoxy ligands undergo efficient C–O scission on Si(1 0 0), leaving carbonaceous fragments embedded in the interfacial layer. In contrast, after small deposits on Si(1 1 1) stable t-butoxy groups are found. These are consumed upon further deposition. Stable methyl and, possibly, also hydroxyl groups are found on both surfaces within a wide film thickness range.

The growth and thermal stability of ultrathin ZrO2 films on the Si-rich Si(0001)-(3 x 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 degrees C yields tetragonal ZrO2. An interface is formed between the ZrO2 film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O-2. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO2 and ZrO2 occurs, possibly under the formation of silicate. The alignment of the ZrO2 and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 degrees C does not lead to decomposition of the tetragonal ZrO2 (t-ZrO2) but changes are observed within the interface region. After annealing to 1000 degrees C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO2 remnants, metallic Zr silicide and Si aggregates.

The insertion of lithium in anatase TiO2 nanoparticles under ultrahigh vacuum (UHV) conditions is studied using x-ray absorption spectroscopy (XAS) and resonant photoelectron spectroscopy (RPES) at the Ti L2,3 edge. It is demonstrated that XAS can be used to monitor the separation into an anatase phase and a lithium titanate phase of formal stoichiometry Li0.5TiO2. The initial state properties of the Ti 3d states of the lithium titanate phase are investigated using ab initio electronic structure calculations. The calculations show a correlation driven separation of Ti 3d states from the conduction band in agreement with previous studies. It is shown that Ti in different oxidation states (Ti3+ and Ti4+) is formed as a direct consequence of the electron-electron interaction. RPES and XAS spectra confirm the presence of electronically inequivalent Ti sites. The site-sensitivity of the RPES spectra at selected electron binding energies is found to be consistent with the calculations.