Fabricating complex transition metal oxides with a tuneable band gap without compromising their intriguing physical properties is a longstanding challenge. Here we examine the layered ferroelectric bismuth titanate and demonstrate that, by site-speci
fic substitution with the Mott insulator lanthanum cobaltite, its band gap can be narrowed as much as one electron volt, while remaining strongly ferroelectric. We find that when a specific site in the host material is preferentially substituted, a split-off state responsible for the band gap reduction is created just below the conduction band of bismuth titanate. This provides a route for controlling the band gap in complex oxides for use in emerging oxide opto-electronic and energy applications.
The interfacial screening charge that arises to compensate electric fields of dielectric or ferroelectric thin films is now recognized as the most important factor in determining the capacitance or polarization of ultrathin ferroelectrics. Here we in
vestigate using aberration-corrected electron microscopy and density functional theory how interfaces cope with the need to terminate ferroelectric polarization. In one case, we show evidence for ionic screening, which has been predicted by theory but never observed. For a ferroelectric film on an insulating substrate, we found that compensation can be mediated by interfacial charge generated, for example, by oxygen vacancies.
A combined experimental and computational investigation of coupling between polarization and epitaxial strain in highly polar ferroelectric PbZr_0.2Ti_0.8O_3 (PZT) thin films is reported. A comparison of the properties of relaxed (tetragonality c/a =
1.05) and highly-strained (c/a = 1.09) epitaxial films shows that polarization, while being amongst the highest reported for PZT or PbTiO_3 in either film or bulk forms (P_r = 82 microC/cm^2), is almost independent of the epitaxial strain. We attribute this behavior to a suppressed sensitivity of the A-site cations to epitaxial strain in these Pb-based perovskites, where the ferroelectric displacements are already large, contrary to the case of less polar perovskites, such as BaTiO_3. In the latter case, the A-site cation (Ba) and equatorial oxygen displacements can lead to substantial polarization increases.
