Defect design in ferroelectrics -- new insights on agglomeration

Abstract: Functional properties of ferroelectrics and their change with time depend crucially on the defect structure. In particular, point defects and bias fields induced by defect dipoles modify the field hysteresis and play an important role in fatigue and aging. However, a full understanding on how order, agglomeration and strength of defect dipoles affect phase stability and functional properties is still lacking. To close these gaps in knowledge, we screen these parameters by \textit{ab\ initio} based molecular dynamics simulations with the effective Hamiltonian method for the prototypical ferroelectric material (Ba,Sr)TiO$_3$. Our findings suggest that the {\it{active surface area}} of the defects, rather than the defect concentration is the decisive factor. For a fixed defect concentration, clustering reduces the {\it{active surface area}} and thus the defect-induced changes of phase stability and field hysteresis. Particularly planar agglomerates of defects appear as promising route for the material design as their impact on the field hysteresis can be controlled by the field direction and their impact on the phase stability shows a cross-over with the strength of the defect dipoles. For this agglomeration, we furthermore show that a pinched double-loop field hysteresis allows for large recoverable stored energy which can outperform the response of pristine (Ba,Sr)TiO$_3$ even in its paraelectric phase.