Epitaxial oxide thin films are at the heart of new “oxide electronic” applications, such as excitonic ultraviolet light-emitting diodes and resistive switching memories. Complex oxide films are often grown by pulsed laser deposition (PLD) because the technique is believed to be material agnostic. Here, we show that one of the fundamental premises used to justify the use of PLD, that material is transferred from an ablation target to the film without stoichiometry deviations, is incorrect even when no volatile elements are involved. Even more importantly, the commonly used solution of increasing the laser energy density above a material-specific threshold value to obtain stoichiometric films cannot be used in the case of low carrier density systems such as SrTiO3, where even minute 1018 cm−3 order cation nonstoichiometry can have a dramatic effect on transport. Lattice parameter deviations in oxide films, which are often incorrectly ascribed to oxygen loss, correlate very well with cation nonstoichiometry. We show that proper simultaneous choice of ablation laser fluence and ablation area is essential and often more important than the growth temperature and oxygen pressure for obtaining bulklike properties in oxide heterostructures.

Pulsed laser deposition (PLD) is a good method for growing high-quality functional oxide thin films because of the technical simplicity and the ease with which deposition can be switched from one material to another. However, the repeatability of film quality is often hard to achieve, especially when using several different PLD systems. Here we report the steps that we have taken to grow nearly bulk-equivalent defect-free thin films, with SrTiO3 as an example, by using PLD in a reproducible fashion. The ablation laser fluence was found to have a very strong effect on the lattice constant and defect structure of the films. Nonstoichiometric transfer of material from the ablation target was observed when either the laser fluence or the beam spot area was inadequate.

In situ thickness-dependent photoemission spectroscopy (PES) has been performed on SrRuO3 (SRO) layers deposited on SrTiO3 substrates to study the structure-induced evolution of the electronic structure. The PES spectra showing the existence of two critical film thicknesses reveal that a metal-insulator transition occurs at a film thickness of 4–5 monolayers (ML) and the evolution of Ru 4d-derived states around the Fermi level (EF) saturates at about 15 ML. The observed spectral behavior well matches the electric and magnetic properties and thickness-dependent evolution of surface morphology of the ultrathin SRO films. These experimental results suggest the importance of the disorder associated with the unique growth-mode transition in SRO films.

The occupied and unoccupied in-gap electronic states of a Rh-doped SrTiO3 photocatalyst were investigated by X-ray emission spectroscopy and X-ray absorption spectroscopy for different Rh impurity valence states and doping levels. An unoccupied midgap Rh4+ acceptor state was found 1.5 eV below the SrTiO3 conduction band minimum. Both Rh4+ and Rh3+ dopants were found to have an occupied donor level close to the valence band maximum of SrTiO3. The density of states obtained from first-principles calculations show that all observed spectral features can be assigned to electronic states of substitutional Rh at the Ti site and that Rh:SrTiO3 is an unusual titanate compound with a characteristic p-type electronic structure. The Rh doping results in a large decrease of the bandgap energy, making Rh:SrTiO3 an attractive material for use as a visible-light-driven H2-evolving photocatalyst in a solar water splitting reaction.

We have studied the electronic structure of epitaxially grown thin films of La1−xSrxFeO3 by insitu photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS) measurements. The Fe 2p and valence-band PES spectra and the O 1s XAS spectra of LaFeO3 have been successfully reproduced by configuration-interaction cluster-model calculation and, except for the satellite structure, by band-structure calculation. From the shift of the binding energies of core levels, the chemical potential was found to be shifted downward as x was increased. Among the three peaks in the valence-band spectra of La1−xSrxFeO3, the peak nearest to the Fermi level (EF ), due to the "eg band", was found to move toward EF and became weaker as x was increased, whereas the intensity of the peak just above EF in the O 1s XAS spectra increased with x. The gap or pseudogap at EF was seen for all values of x. These results indicate that changes in the spectral line shape around EF are dominated by spectral weight transfer from below to above EF across the gap and are therefore highly non-rigid-band-like.