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 degrees 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 Ce3+/ Ce4+ 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 degrees C showing marked changes of the Ce oxidation state when exposed to both reducing and oxidizing gas atmospheres at moderate temperature (300 degrees C), while the Ce valence is weakly affected for the 1000 degrees 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 degrees C and are fundamental to further improve sputtered GDC thin film performance in energy devices.