Disappearance of ferroelectric critical thickness in epitaxial ultrathin BaZrO3 films

The intrinsic critical ferroelectric thickness of epitaxial ultrathin capacitors of incipient ferroelectric BaZrO3 (BZO) films with realistic SrRuO3 (SRO) electrodes is investigated by first-principles calculations based on density functional theory. We reveal that polarization can stably exist even in one-unit-cell thick BZO films, i.e., absence of critical thickness, whereas the widely investigated proper ferroelectrics like BaTiO3 and SrTiO3 films have no polarization. The influences of realistic ferroelectric-electrode interface and misfit strain on the ionic and electronic structures of the BZO-SRO thin film system have been examined under the short-circuited boundary condition. It is found that the ionic polarization of conductive SRO electrodes can effectively strengthen the screening of bound charges at the interface, which greatly reduces the depolarization field in the BZO films. Furthermore, the epitaxial misfit strain remarkably enhances the polarization through the enhancement of hybridization of Zr and O electron orbitals, resulting in the disappearance of ferroelectric critical thickness. Our findings are beyond the critical thickness of proper ferroelectrics and are thus promising for future nanometer-scale ferroelectric device such as high-density ferroelectric memory.