While commonly used piezoelectric materials contain lead, non-hazardous, high-performance piezoelectrics are yet to be discovered. Charged domain walls in ferroelectrics are considered inactive with regards to the piezoelectric response and, therefore, are largely ignored in this search. Here we demonstrate a mechanism that leads to a strong enhancement of the dielectric and piezoelectric properties in ferroelectrics with increasing density of charged domain walls. We show that an incomplete compensation of bound polarization charge at these walls creates a stable built-in depolarizing field across each domain leading to increased electromechanical response. Our model clarifies a long-standing unexplained effect of domain wall density on macroscopic properties of domain-engineered ferroelectrics. We show that non-toxic ferroelectrics like BaTiO3 with dense patterns of charged domain walls are expected to have strongly enhanced piezoelectric properties, thus suggesting a new route to high-performance, lead-free ferroelectrics.
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