Site occupancy effects of Mg impurities in BaTiO3

A first-principles based atomistic model is developed to investigate intrinsic effects of Mg incorporation into A- and B-sites of BaTiO3. We find that the replacement of Ba by Mg at A-site positions generates local electric dipoles due to Mg off-centering along [001] directions, which increase the Curie temperature and decrease the cell volume. The inverse dependence is observed for B-site doped compositions, where the defect dipoles decrease the Curie temperature and expand the volume. Temperature-composition phase diagrams are constructed for both site locations and the effect of the two types of defects on the switching process is investigated. The theoretical predictions are used to shed light on experimental results of Mg-doped ceramics manufactured to induce a given occupation site. The comparison indicates that the incorporation of Mg into the B-site is thermodynamically favorable whereas the properties observed for the A-site ceramics cannot be explained from the intrinsic effects described by the model. •Site occupancy effects of Mg2+ in BaTiO3 are investigated from atomistic simulations.•Temperature-composition phase diagrams are constructed.•Theoretical results are confronted with experimental data from Mg-doped ceramics.•The incorporation of Mg2+ into the B-site is thermodynamically favorable.•Experimental results for A-site doping cannot be explained from intrinsic effects.