Expanding the activity of wide bandgap semiconductors from the UV into the visible range has become a central goal for their application in green solar photocatalysis. The hybrid plasmonic/semiconductor system, based on silver nanoparticles (Ag NPs) embedded in a film of CeO 2 , is an example of a functional material developed with this aim. In this work, we take advantage of the chemical sensitivity of free electron laser (FEL) time-resolved soft X-ray absorption spectroscopy (TRXAS) to investigate the electron transfer process from the Ag NPs to the CeO 2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (<200 fs) of the Ce N 4,5 absorption edge allowed us to conclude that the excited Ag NPs transfer electrons to the Ce atoms of the CeO 2 film through a highly efficient electron-based mechanism. These results demonstrate the potential of FEL-based TRXAS measurements for the characterization of energy transfer in novel hybrid plasmonic/semiconductor materials.

We investigate the interaction between molecular hydrogen and ultrathin epitaxial CeO2 films modified with a 2% concentration of Cu atoms using X-ray photoemission spectroscopy (XPS) during thermal reduction cycles in H2. The XPS measurements are combined with density functional theory calculations to obtain further insight into the observed modifications of the film surface. Our results show that the presence of Cu atoms decreases the barrier for H2 dissociation in comparison to that on pure ceria surfaces, leading to the formation of surface OH groups after exposure to H2. Moreover, surface oxygen vacancies are generated already at mild temperatures (470 K), most likely via water formation and desorption. The presence of surface oxygen vacancies and hydroxyls contributes to the observed large increase in surface Ce3+ concentration with increasing reduction temperature. In spite of these atomic scale modifications, the surface morphology observed by scanning tunneling microscopy remains substantially unchanged on the length scale of tens of nm.

Pre‐formed Ag nanoparticles (NPs) and Ag@CaF2 core–shell NPs are physically synthesized using DC magnetron‐based NP source and deposited on Si‐SiOx wafers. The samples are prepared by co‐depositing Ag nanoparticles and CaF2 produced by an evaporation source, or by sequential deposition method, i.e., by depositing in a sequence a CaF2 buffer layer, the Ag NPs generated by the NP source and a capping CaF2 layer. The supported films are characterized by Scanning Electron Microscopy (SEM), X‐ray Photoelectron Spectroscopy (XPS), and Surface Differential Reflectivity (SDR). SEM shows that Ag NPs deposited directly on Si‐SiOx tend to diffuse and to agglomerate, affecting the size distribution of the nanostructures. The presence of a CaF2 buffer layer between Ag and Si‐SiOx limits this effect, while XPS reveals electrical charging, caused by the insulating nature of the CaF2 continuous film. The surface plasmon resonance behavior for different samples is analyzed using SDR with p‐polarized light. There is a clear evidence of a blue shift in the plasmon excitation due to the presence of CaF2 on Si, which can represent a potential advantage for the technological applications in photovoltaics and optoelectronics.