Abstract
Ferroelectric perovskites present a switchable spontaneous polarization and are promising energy-efficient device components for digital information storage. Full control of the ferroelectric polarization in ultrathin films of ferroelectric perovskites needs to be achieved in order to apply this class of materials in modern devices. However, ferroelectricity itself is not well understood in this nanoscale form, where interface and surface effects become particularly relevant and where loss of net polarization is often observed. In this work, we show that the precise control of the structure of the top surface and bottom interface of the thin film is crucial toward this aim. We explore the properties of thin films of the prototypical ferroelectric lead titanate (PbTiO(3)) on a metallic strontium ruthenate (SrRuO(3)) buffer using a combination of computational (density functional theory) and experimental (optical second harmonic generation) methods. We find that the polarization direction and strength are influenced by chemical and electronic processes occurring at the epitaxial interface and at the surface. The polarization is particularly sensitive to adsorbates and to surface and interface defects. These results point to the possibility of controlling the polarization direction and magnitude by engineering specific interface and surface chemistries.