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Epitaxial CeO 2 films with different thickness were grown on Y 2 O 3 stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO 2 films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce 4+ to Ce 3+ at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also for understanding ceria catalytic properties.
