Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria doped ceria thin films as catalytic coatings

Samaria doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films` oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, it raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM First Order Reversal Curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. Implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electro-catalytic applications