Impact of Chemical Clustering on the Structural, Topological, and Functional Properties of Ba(Zr$_x$Ti$_{1-x}$)O$_3$: An Atomistic Simulation Study

Abstract

Barium zirconate titanate, Ba(Zr$_x$Ti$_{1-x}$)O$_3$ (BZT), is a leading lead-free candidate for high-performance electronic components due to its highly tunable ferroelectric-to-relaxor transition. In this study, we employ molecular dynamics simulations to investigate the effects of local chemical clustering on the structural and functional properties of BZT in both ferroelectric (x = 0.2) and relaxor (x = 0.4) regimes. Crucially, we demonstrate that Zr clustering induces a significant enhancement of local polarization across both compositions. Rather than a purely volume-driven effect, this enhancement is fundamentally governed by a spatial redistribution of local structural phases (rhombohedral, orthorhombic, and tetragonal); Zr segregation forms larger, continuous Ti-rich regions that expand highly polar rhombohedral domains and foster cooperative dipolar alignment. This cooperative coupling thermally stabilizes the local polar order, systematically elevating the Curie, maximum permittivity, and Burns temperatures. Focusing on the relaxor composition (x = 0.4), chemical segregation promotes the formation of resilient, swirling polar topological textures,categorized into vortices circulating around Zr-rich clusters and interstitial vortices localized within the Ti-rich matrix. These topological structures act as effective pinning barriers against polarization reversal, driving pronounced electrical hardening with elevated coercive fields. Ultimately, these findings establish a quantitative link between nanoscale compositional heterogeneity, polar domain topology, and macroscopic performance, providing a robust framework for engineering lead-free perovskites via local chemical order control.