Evidence of phase coexistence in hydrothermally synthesized K_0.5Na_0.5NbO₃nanofibers

The argument of phase coexistence in the lead-free piezoelectric perovskite K_0.5Na_0.5NbO₃(KNN) has led to significant discrepancies in the interpretation of its exact crystalline structure in the literature. In this work, the structural details of hydrothermally prepared KNN nanofibres and microcubes were investigated by a combination of high resolution transmission electron microscopy (TEM), solid-state²³Na and⁹³Nb nuclear magnetic resonance (NMR) spectroscopy and two-dimensional²³Na 3QMAS NMR. Although powder X-ray diffraction yielded an average orthorhombic structure for both morphologies, high resolution TEM revealed mixed phases of orthorhombic (O) and monoclinic (M) symmetry with a growth direction of [001] and [110], respectively, in individual KNN nanofibres. Consistent with the TEM analysis, solid-state²³Na NMR indicated a distribution of multiple Na sites in the KNN nanofibers, which were not observed in the KNN microcubes. This study provided microscopic evidence of phase coexistence in KNN nanofibers and suggested that a two-phase concomitant state might be highly dependent on the size and morphologies of the KNN nanostructures.