1. Department of Chemistry and Laboratory for Research on the Structure of Matter, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA

Correspondence to: Andrew M. Rappe Correspondence and requests for materials should be addressed to A.M.R. (e-mail: Email: rappe@sas.upenn.edu).

Abstract

The Pb(Zr,Ti)O₃ (PZT) disordered solid solution is widely used in piezoelectric applications owing to its excellent electromechanical properties. Six different structural phases have been observed for PZT at ambient pressure, each with different lattice parameters and average electric polarization. It is of significant interest to understand the microscopic origin of the complicated phase diagram and local structure of PZT^{1, 2, 3, 4, 5, 6, 7, 8}. Here, using density functional theory calculations, we show that the distortions of the material away from the parent perovskite structure can be predicted from the local arrangement of the Zr and Ti cations. We use the chemical rules obtained from density functional theory to create a phenomenological model to simulate PZT structures. We demonstrate how changes in the Zr/Ti composition give rise to phase transitions in PZT through changes in the populations of various local Pb atom environments.