Predicting morphotropic phase boundary locations and transition temperatures in Pb- and Bi-based perovskite solid solutions from crystal chemical data and first-principles calculations

Abstract

Using data obtained from first-principles calculations, we show that the position of the morphotropic phase boundary (MPB) and transition temperature at MPB in ferroelectric perovskite solutions can be predicted with quantitative accuracy from the properties of the constituent cations. We find that the mole fraction of ${\mathrm{PbTiO}}_3$ at MPB in $\mathrm{Pb}\left(B^{\prime }{B}^{″}\right){\mathrm{O}}_3–{\mathrm{PbTiO}}_3$ , ${\mathrm{BiBO}}_3–{\mathrm{PbTiO}}_3$ , and $\mathrm{Bi}\left(B^{\prime }{B}^{″}\right){\mathrm{O}}_3–{\mathrm{PbTiO}}_3$ exhibits a linear dependence on the ionic size (tolerance factor) and the ionic displacements of the $B$ cations as found by density-functional-theory calculations. This dependence is due to competition between the local repulsion and $A$ -cation displacement alignment interactions. Inclusion of first-principles displacement data also allows accurate prediction of transition temperatures at the MPB. The obtained structure-property correlations are used to predict morphotropic phase boundaries and transition temperatures in as yet unsynthesized solid solutions.