We report the study of anatase TiO(001)-oriented thin films grown by pulsed laser deposition on LaAlO(001). A combination of in situ and ex situ methods has been used to address both the origin of the Ti-localized states and their relationship with the structural and electronic properties on the surface and the subsurface. Localized in-gap states are analyzed using resonant X-ray photoelectron spectroscopy and are related to the Ti electronic configuration, homogeneously distributed over the entire film thickness. We find that an increase in the oxygen pressure corresponds to an increase in Ti only in a well-defined range of deposition pressure; outside this range, Ti and the strength of the in-gap states are reduced.

Pump-and-probe photoelectron spectroscopy (PES) with femtosecond pulsed sources opens new perspectives in the investigation of the ultrafast dynamics of physical and chemical processes at the surfaces and interfaces of solids. Nevertheless, for very intense photon pulses a large number of photoelectrons are simultaneously emitted and their mutual Coulomb repulsion is sufficiently strong to significantly modify their trajectory and kinetic energy. This phenomenon, referred as space-charge effect, determines a broadening and shift in energy for the typical PES structures and a dramatic loss of energy resolution. In this article we examine the effects of space charge in PES with a particular focus on time-resolved hard X-ray (∼10 keV) experiments. The trajectory of the electrons photoemitted from pure Cu in a hard X-ray PES experiment has been reproduced through N-body simulations and the broadening of the photoemission core-level peaks has been monitored as a function of various parameters (photons per pulse, linear dimension of the photon spot, photon energy). The energy broadening results directly proportional to the number N of electrons emitted per pulse (mainly represented by secondary electrons) and inversely proportional to the linear dimension a of the photon spot on the sample surface, in agreement with the literature data about ultraviolet and soft X-ray experiments. The evolution in time of the energy broadening during the flight of the photoelectrons is also studied. Despite its detrimental consequences on the energy spectra, we found that space charge has negligible effects on the momentum distribution of photoelectrons and a momentum broadening is not expected to affect angle-resolved experiments. Strategy to reduce the energy broadening and the feasibility of hard X-ray PES experiments at the new free-electron laser facilities are discussed

In the rapidly growing field of spintronics, simultaneous control of electronic and magnetic properties is essential, and the perspective of building novel phases is directly linked to the control of tuning parameters, for example, thickness and doping. Looking at the relevant effects in interface-driven spintronics, the reduced symmetry at a surface and interface corresponds to a severe modification of the overlap of electron orbitals, that is, to a change of electron hybridization. Here we report a chemically and magnetically sensitive depth-dependent analysis of two paradigmatic systems, namely La1−xSrxMnO3 and (Ga,Mn)As. Supported by cluster calculations, we find a crossover between surface and bulk in the electron hybridization/correlation and we identify a spectroscopic fingerprint of bulk metallic character and ferromagnetism versus depth. The critical thickness and the gradient of hybridization are measured, setting an intrinsic limit of 3 and 10 unit cells from the surface, respectively, for (Ga,Mn)As and La1−xSrxMnO3, for fully restoring bulk properties.

The combination of photoemission spectroscopies, infrared and UV-VIS absorption, and electric measurements has allowed to clarify the mechanisms governing the conductivity and the electronic properties of Al-doped ZnO (AZO) films in a wide doping range. The contribution of defect-related in-gap states to conduction has been excluded in optimally doped films (around 4 at. %). The appearance of gap states at high doping, the disappearance of occupied DOS at Fermi level, and the bands evolution complete the picture of electronic structure in AZO when doped above 4 at. %. In this situation, compensating defects deplete the conduction band and increase the electronic bandgap of the material. Electrical measurements and figure of merit determination confirm the high quality of the films obtained by magnetron sputtering, and thus allow to extend their properties to AZO films in general.