Highly oriented ionic conductor gadolinium-doped CeO2−δ (Ce0.8Gd0.2O2−δ) thin films have been grown on single-crystal (001) MgO substrates by pulsed-laser ablation. The films are highly c-axis oriented with cube-on-cube epitaxy, as shown by x-ray diffraction and electron microscopy. The interface relationship is, surprisingly, found to be (001)film//(001)sub and [100]film//[100]sub with an extremely large lattice misfit of more than 28%. Ac impedance measurements in the temperature range of 500 to 800 °C reveal that electrical conductivity is predominantly ionic over a very broad oxygen partial pressure range from pO2 from 1×10−19 atm to 1 atm. The activation energy Ea for ionic conductivity measured on unannealed films is 0.86 eV, but after heat treatment, Ea decreases to 0.74 eV.
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