Refreshing Piezoelectrics: Distinctive Role of Manganese in Lead-Free Perovskites

Driven by an ever-growing demand for environmentally compatible materials, the past two decades have witnessed the booming development in the field of piezoelectrics. To maximally explore the potential of lead-free piezoelectrics, chemical doping could be an effective approach, referenced from tactics adopted in lead-based piezoelectrics. Herein, we reveal the distinct role of manganese in a promising lead-free perovskite (K, Na)NbO₃ (denoted by KNN) in comparison to that in market-dominating lead-based counterparts [Pb(Zr, Ti)O₃, PZT]. In contrast to the scenario in PZT, manganese doping in KNN results in tremendously improved piezoelectric coefficient d₃₃ by nearly 200%, whereas the same doping species in PZT deteriorates the d₃₃ down to less than 30% of its original value. The result is rationalized from macroscopic and local electrical characterizations down to atomic-scale visualization. This study demonstrates that there is enormous space to further enhance piezoelectricity in lead-free systems because the chemical doping effect may completely differ in lead-containing and lead-free perovskites.