Kinetic pathways to modulate ferroelectricity in PbZrO₃

Ferroelectric and antiferroelectric oxides represent a fascinating class of functional materials, offering unique polarization switching behaviors and phase transition mechanisms with potential for energy storage and electronic device applications. Any subtle changes in structure or defects can dramatically alter polarization behavior and phase stability. Lead zirconate (PbZrO₃) is a prototypical antiferroelectric, yet stabilizing its ferroelectric state has traditionally relied on compositional substitution or strain engineering, approaches that limit scalability and reproducibility. Here, we present a deterministic strategy to achieve phase selectivity in lead-rich PbZrO₃ thin films by controlling deposition kinetics during pulsed laser deposition. By systematically varying the growth rate, we uncover how defect formation and charge compensation pathways can be tuned to stabilize either ferroelectric or antiferroelectric states, without altering composition. Structural, spectroscopic, and functional characterizations highlight clear correlations between growth kinetics, defect landscapes, and ferroic order. These findings not only provide fresh insights into kinetic control of ferroic phases but also establish a scalable pathway for phase engineering in complex oxides, beyond compositional modifications, providing a deterministic and scalable route for functional tuning, with direct implications for energy-efficient capacitors and switching devices.