Beyond phase boundaries: atomic mechanisms governing structure and property variations in (K, Na)NbO3-based ferroelectrics

Chemical dopants-induced phase boundary engineering has boosted electrical properties of (K, Na)NbO₃-based piezoceramics, yet the underlying mechanisms governing these improvements remain unclear. Here, we elucidate these mechanisms through comprehensive multi-scale structural analysis (atomic-to-nanoscale-to-mesoscale) on two representative solid-solutions, namely (K, Na, Li)NbO₃ and (K, Na)NbO₃-(Bi_0.5Na_0.5)ZrO₃. By utilizing neutron pair distribution function analysis, scanning transmission electron microscope, first-principle calculations, and phase-field simulations, our results reveal distinct atomic-scale mechanism underlying phase boundary engineering. In (K, Na, Li)NbO₃, convergent off-center displacements of Li atoms induce an interplay between displacive and order-disorder phase transition; while in (K, Na)NbO₃-(Bi_0.5Na_0.5)ZrO₃, divergent off-center displacements of Bi atoms trigger a predominant order-disorder type phase transition. These atomic-scale structural characteristics directly correlate with mesoscopic ferroelectric domains and ultimately determine macroscopic electrical properties. This work elucidates the role of chemical dopants in phase boundary engineering from a multi-scale perspective, establishing a framework for designing lead-free piezoceramics with enhanced electrical properties and advancing the development of eco-friendly piezoceramics.