Evidence for enhanced oxygen surface exchange reaction in nanostructured Gd2O3-doped CeO2 films

The effect of microstructure of Gd₂O₃-doped CeO₂ (GDC) films on oxygen surface exchange and diffusion is reported. Epitaxial GDC (10 mol% Gd) films up to 1 μm in thickness are prepared using pulsed laser deposition on (100) yttria-stabilized zirconia single-crystal substrates and subjected to high-temperature annealing at 1300 °C in air to induce microstructural modifications. Characterization using atomic force microscopy and transmission electron microscopy reveals granular morphologies comprised of densely packed columnar nanostructures for the as-grown GDC films; however, significant microstructural reconstruction of the entire GDC layer occurs after high-temperature annealing. (18)O isotope exchange depth profiling with dynamic secondary ion mass spectroscopy is employed to evaluate the oxygen surface exchange coefficient k* and the diffusion coefficient D* at T = 600 °C. The as-grown GDC exhibits up to 10 times higher k* than the annealed film. The strong differences in oxygen surface reaction are correlated to the observed film properties including surface microstructure and cerium oxidation state as evaluated using electron energy loss spectroscopy in scanning transmission electron microscopy.