Crystalline heterogeneity in single ferroelectric nanocrystals revealed by polarized nonlinear microscopy

Ferroelectric nanocrystals have considerable interest for applications in nanophotonics, optical memories and bio-imaging. Their crystalline nature at the nanoscale remains however poorly known, mostly because structural investigation tools on single nanocrystals are lacking. In this work we apply polarization resolved second harmonic generation (P-SHG) imaging on isolated Barium Titanate (BaTiO₃) nanocrystals to unravel their crystalline nature, exploiting the sensitivity of polarized SHG to local non-centrosymmetry and nanocrystals surface responses. We evidence crystalline heterogeneities in BaTiO₃ nanocrystals manifested by a centrosymmetric shell around the tetragonal core of the crystals, corroborating hypotheses from previous ensemble structural investigations. This study shows that in contrast to bulk materials, nanocrystals exhibit a complex composition, which is seen to be reproducible among nanocrystals. P-SHG appears furthermore as a powerful methodology that reports structural behaviors in nanoscale dielectrics materials, at the individual nanoparticle scale.