Gdolinia doped ZrO2 and CeO2 multi-layer films were deposited on alpha-Al2O3 (0001) using oxygen-plastria-assisted molecular-beam epitaxy. Oxygen vacancies and Gd dopant distributions were investigated in these multi-layer films using X-ray diffraction (XRD), conventional and high-resolution transmission electron microscopy (HRTEM), annular dark-field imaging in scanning transmission electron microscopy (STEM), X-ray energy dispersive spectroscopy (EDS) elemental mapping and X-ray photoelectron spectroscopy (XPS) depth profiling. EDS and XPS depth profiling reveal that the Gd concentration in the ZrO2 layer is lower than that in the CeO2 layer. As a result, a higher oxygen vacancy concentration exists in the CeO2 layers compared to that in the ZrO2 layers. In addition, Gd is found to segregate only at the interfaces formed during the deposition of CeO2 layers on ZrO2 layers. On the other hand, the interfaces formed during the deposition of ZrO2 layers on CeO2 layers did not show any Gd segregation. The Gd segregation behavior at every other interface is believed to be associated with the low solubility of Gd in ZrO2. (c) 2006 Elsevier B.V. All rights reserved.