Local Enhancement of Polarization at PbTiO₃/BiFeO₃ Interfaces Mediated by Charge Transfer

Ferroelectrics hold promise for sensors, transducers, and telecommunications. With the demand of electronic devices scaling down, they take the form of nanoscale films. However, the polarizations in ultrathin ferroelectric films are usually reduced dramatically due to the depolarization field caused by incomplete charge screening at interfaces, hampering the integrations of ferroelectrics into electric devices. Here, we design and fabricate a ferroelectric/multiferroic PbTiO₃/BiFeO₃ system, which exhibits discontinuities in both chemical valence and ferroelectric polarization across the interface. Aberration-corrected scanning transmission electron microscopic study reveals an 8% elongation of out-of-plane lattice spacing associated with 104%, 107%, and 39% increments of δ_Ti, δ_O1, and δ_O2 in the PbTiO₃ layer near the head-to-tail polarized interface, suggesting an over ∼70% enhancement of polarization compared with that of bulk PbTiO₃. Besides that in PbTiO₃, polarization in the BiFeO₃ is also remarkably enhanced. Electron energy loss spectrum and X-ray photoelectron spectroscopy investigations demonstrate the oxygen vacancy accumulation as well as the transfer of Fe³⁺ to Fe²⁺ at the interface. On the basis of the polar catastrophe model, FeO₂/PbO interface is determined. First-principles calculation manifests that the oxygen vacancy at the interface plays a predominate role in inducing the local polarization enhancement. We propose a charge transfer mechanism that leads to the remarkable polarization increment at the PbTiO₃/BiFeO₃ interface. This study may facilitate the development of nanoscale ferroelectric devices by tailing the coupling of charge and lattice in oxide heteroepitaxy.