Multilayered heterostructures of CeSmO and YZrO of a high crystallographic quality were fabricated on (001)-oriented MgO single crystal substrates. Keeping the total thickness of the heterostructures constant, the number of ceria-zirconia bilayers was increased while reducing the thickness of each layer. At each interface Ce was found primarily in the reduced, 3+ oxidation state in a layer extending about 2 nm from the interface. Concurrently, the conductivity decreased as the thickness of the layers was reduced, suggesting a progressive confinement of the charge transport along the YSZ layers. The comparative analysis of the in-plane electrical characterization suggests that the contribution to the total electrical conductivity of these interfacial regions is negligible. For the smallest layer thickness of 2 nm the doped ceria layers are electrically insulating and the ionic transport only occurs through the zirconia layers. This is explained in terms of a reduced mobility of the oxygen vacancies in the highly reduced ceria.
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