Switching Lead for Tin in PbHfO₃ : Noncubic Structure of SnHfO₃

The removal of lead from commercialized perovskite-oxide-based piezoceramics has been a recent major topic in materials research owing to legislation in many countries. In this regard, Sn(II)-perovskite oxides have garnered keen interest due to their predicted large spontaneous electric polarizations and isoelectronic nature for substitution of Pb(II) cations. However, they have not been considered synthesizable owing to their high metastability. Herein, the perovskite lead hafnate, i.e., PbHfO₃ in space group Pbam, is shown to react with SnClF at a low temperature of 300 °C, and resulting in the first complete Sn(II)-for-Pb(II) substitution, i.e. SnHfO₃ . During this topotactic transformation, a high purity and crystallinity is conserved with Pbam symmetry, as confirmed by X-ray and electron diffraction, elemental analysis, and ¹¹⁹ Sn Mössbauer spectroscopy. In situ diffraction shows SnHfO₃ also possesses reversible phase transformations and is potentially polar between ≈130-200 °C. This so-called 'de-leadification' is thus shown to represent a highly useful strategy to fully remove lead from perovskite-oxide-based piezoceramics and opening the door to new explorations of polar and antipolar Sn(II)-oxide materials.