Phonons and oxygen diffusion in Bi2O3 and (Bi0.7Y0.3)2O3

Abstract

We report investigation of phonons and oxygen diffusion in Bi2O3 and (Bi0.7Y0.3)2O3. The phonon spectra have been measured in Bi2O3 at high temperatures up to 1083 K using inelastic neutron scattering. Ab initio calculations have been used to compute the individual contributions of the constituent atoms in Bi2O3 and (Bi0.7Y0.3)2O3 to the total phonon density of states. Our computed results indicate that as temperature is increased, there is a complete loss of sharp peak structure in the vibrational density of states. Ab initio molecular dynamics simulations show that even at 1000 K in δ-phase Bi2O3, Bi–Bi correlations remain ordered in the crystalline lattice while the correlations between O–O show liquid like disordered behavior. In the case of (Bi0.7Y0.3)2O3, the O–O correlations broadened at around 500 K indicating that oxygen conductivity is possible at such low temperatures in (Bi0.7Y0.3)2O3 although the conductivity is much less than that observed in the undoped high temperature δ-phase of Bi2O3. This result is consistent with the calculated diffusion coefficients of oxygen and observation by quasielastic neutron scattering experiments. Our ab initio molecular dynamics calculations predict that macroscopic diffusion is attainable in (Bi0.7Y0.3)2O3 at much lower temperatures, which is more suited for technological applications. Our studies elucidate the easy directions of diffusion in δ-Bi2O3 and (Bi0.7Y0.3)2O3.