Integrated experimental and modeling study of the ionic conductivity of samaria-doped ceria thin films

Oxygen diffusion and ionic conductivity of samaria-doped ceria (SDC) thin films have been studied as a function of composition using experiment and atomistic simulation. SDC thin films were grown on Al2O3 (0001) substrates by oxygen plasma-assisted molecular beam epitaxy (OPA-MBE) technique. The experimental results show a peak in electrical conductivity of SDC at 15 mol% SmO1.5. The ionic conductivity obtained from molecular dynamics simulation of the same system shows a peak at about 13 mol% SmO1.5. The activation energy for oxygen diffusion was found to be in the range from 0.8 to 1 eV by simulations depending on the SmO1.5 content, which compares well with the range from 0.6 to 0.9 eV given by the experimental work. The simulations also show that oxygen vacancies prefer Sm3+ ions as first neighbors over Ce4+ ions. The present results reveal that the optimum samaria content for ionic conductivity in single crystals of SDC is less than that in polycrystals, which can be related to the preferential segregation of dopant cations to grain boundaries in polycrystals.

► Integrated experiment and modeling study of single crystal samaria-doped ceria.
► Activation energy for oxygen diffusion is in the range from about 0.8 to 1 eV.
► Conductivity peak at lower dopant content than value reported for polycrystals.
► Oxygen vacancies prefer Sm3+ dopants as first neighbors.
► Dopant segregation may explain differences between single crystals and polycrystals.