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Relationship between local structure and phase transitions of a disordered solid solution


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 PZT1,2,3,4,5,6,7,8. 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.

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Figure 1: Pair distribution functions (PDFs) for PZT with 50% Zr/50% Ti.
Figure 2: Projection of the 4 × 2 × 1 50/50 supercell DFT PZT structure on the xy plane.
Figure 3


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We thank T. Egami, W. Dmowski and P. K. Davies for discussions and for sharing PDF data. This work was supported by the Office of Naval Research and the National Science Foundation. Computational support was provided by the High-Performance Computing Modernization Office of the Department of Defense and the Center for Piezoelectric Design. A.M.R. thanks the Camille and Henry Dreyfus Foundation for support.

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Correspondence to Andrew M. Rappe.

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Grinberg, I., Cooper, V. & Rappe, A. Relationship between local structure and phase transitions of a disordered solid solution. Nature 419, 909–911 (2002).

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