Negative‐Pressure‐Induced Large Polarization in Nanosized PbTiO₃

Ferroelectric materials usually undergo decay with particle size decreasing into the nanoscale. At the critical value, the crystal structure undergoes a transition from the ferroelectric to paraelectric phase and the ferroelectricity vanishes. It is a big issue to sufficiently maintain strong ferroelectricity at the nanoscale. Herein, it is reported that synthesized 0D freestanding PbTiO₃ nanoparticles (NPs) present negative pressure along the c axis (Δc/c_bulk × 100% = -2.406), inducing large spontaneous polarization P_S (71.2 µC cm^-2 in 12 nm). Further local structural studies by atomic pair distribution functions and extended X-ray absorption fine structure indicate the structural evolution of nanosized PbTiO₃ . High-angle annular dark-field STEM images reveal the existence of preponderant PbO-terminations on the surface of the PbTiO₃ NPs. Ab initio calculation reveals the enhanced hybridization between Pb and O ions, which gives rise to the negative pressure and tensile stress to stabilize the high tetragonality and large polarization. The present work demonstrates an untraditional route to enhance the ferroelectricity and related properties in functional nanostructured materials, being of significance to nanodevices.