Experimental evidence of tunable space-charge-layer-induced electrical properties of nanocrystalline ceria thin filmsElectronic supplementary information (ESI) available. See DOI: 10.1039/c3cp43625j

Fully dense nanocrystalline ceria films were successfully deposited on a MgO single crystal by pulsed laser deposition (PLD). The electrical conductivity of the nanocrystalline thin film was 20 times higher than that of the bulk sample. The activation energy of bulk ceria was 2.3 eV, whereas the activation energy of the nanocrystalline sample was only 1.2 eV. After post-annealing at 1273 K in which the grain size of the nanocrystalline thin film increased to ∼400 nm, the electrical conductivity and activation energy of the film were changed similar to those of bulk. These unique electrical properties of the nano-crystalline thin-film can be attributed to the grain size effect, or more specifically, to the space charge layer (SCL) effect. Furthermore, the electrical conductivity of the nanocrystalline thin film became similar to that of the bulk in an extremely reducing atmosphere because of the unusual dependence of the SCL effect on the oxygen partial pressure. Since the space charge layer (SCL) thickness is dependent on the oxygen partial pressure, P O 2 , dependence of electrical conductivity in nano-crystalline ceria follows that of microcrystalline bulk ceria in low P O 2 .