Effects of In-Air Post Deposition Annealing Process on the Oxygen Vacancy Content in Sputtered GDC Thin Films Probed via Operando XAS and Raman Spectroscopy.

We investigate the ionic mobility in room-temperature RF-sputtered gadolinium doped ceria (GDC) thin films grown on industrial solid oxide fuel cell substrates as a function of the air-annealing at 800 and 1000 °C. The combination of X-ray diffraction, X-ray photoelectron spectroscopy, operando X-ray absorption spectroscopy, and Raman spectroscopy allows us to study the different Ce/ Ce ratios induced by the post growth annealing procedure, together with the Ce valence changes induced by different gas atmosphere exposure. Our results give evidence of different kinetics as a function of the annealing temperature, with the sample annealed at 800 °C showing marked changes of the Ce oxidation state when exposed to both reducing and oxidizing gas atmospheres at moderate temperature (300 °C), while the Ce valence is weakly affected for the 1000 °C annealed sample. Raman spectra measurements allow us to trace the responses of the investigated samples to different gas atmospheres on the basis of the presence of different Gd-O bond strengths inside the lattice. These findings provide insight into the microscopic origin of the best performances already observed in SOFCs with a sputtered GDC barrier layer annealed at 800 °C and are fundamental to further improve sputtered GDC thin film performance in energy devices.