First-principles study of the relaxor ferroelectricity of Ba(Zr,Ti)O$_3$

TL;DR

This study uses first-principles calculations to explore the relaxor ferroelectric behavior of Ba(Zr,Ti)O$_3$, revealing how ion arrangements influence properties and providing insights into tuning its ferroelectricity.

Contribution

It presents a detailed first-principles analysis of ion configuration effects on relaxor ferroelectricity in Ba(Zr,Ti)O$_3$, introducing a thermal statistical model for polarization prediction.

Findings

Ion arrangement critically affects ferroelectric properties.

Divergence in properties explains relaxor behavior.

Temperature influences average polarization.

Abstract

Ba(Zr,Ti)O$_3$ is a lead-free relaxor ferroelectric. Using the first-principles method, the ferroelectric dipole moments for pure BaTiO$_3$ and Ba(Zr,Ti)O$_3$ supercells have been studied. All possible ion configurations of BaZr$_{0.5}$Ti$_{0.5}$O$_3$ and BaZr$_{0.25}$Ti$_{0.75}$O$_3$ are constructed in a $2\times2\times2$ supercell. For the half-substituted case, divergence of ferroelectric properties has been found among these structures, which seriously depends on the arrangement of Ti and Zr ions. Thus our results provide a reasonable explanation to the relaxor behavior of Ba(Zr,Ti)O$_3$. In addition, a model based on the thermal statistics gives the averaged polarization for Ba(Zr,Ti)O$_3$, which depends on the temperature of synthesis. Our result is helpful to understand and tune the relaxor ferroelectricity of lead-free Ba(Zr,Ti)O$_3$.