Ionic conductivity of nanocrystalline yttria-stabilized zirconia: Grain boundary and size effects

We report on the effect of grain size on the ionic conductivity of yttria-stabilized zirconia samples synthesized by ball milling. Complex impedance measurements, as a function of temperature and frequency are performed on 10 mol% yttria-stabilized zirconia nanocrystalline samples with grain sizes ranging from 900 to 17 nm. Bulk ionic conductivity decreases dramatically for grain sizes below 100 nm, although its activation energy is essentially independent of grain size. The results are interpreted in terms of a space-charge layer resulting from segregation of mobile oxygen vacancies to the grain-boundary core. The thickness of this space-charge layer formed at the grain boundaries is on the order of 1 nm for large micron-sized grains but extends up to 7 nm when decreasing the grain size down to 17 nm. This gives rise to oxygen vacancies depletion over a large volume fraction of the grain and consequently to a significant decrease in oxide-ion conductivity.