Chemistry of Ferroelectric Surfaces

It has been recognized since the 1950s that the polar and switchable nature of ferroelectric surfaces can potentially lead to polarization direction-dependent surface chemistry. Recent theoretical studies and advances in growing high quality epitaxial ferroelectric thin films have motivated a flurry of experimental studies aimed at creating surfaces with switchable adsorption and catalytic properties, as well as films whose polarization direction switches depending on the gas phase environment. This research news article briefly reviews the key findings of these studies. These include observations that the adsorption strengths, and in certain cases the activation energies for reactions, of polar molecules on the surfaces of ferroelectric materials are sensitive to the polarization direction. For bare ferroelectric surfaces, the magnitudes of these differences are not large, but are still comparable to the energy barrier required to switch the polarization of approximately 10 nm thick films. Highlights of a recent study where chemical switching of a thin film ferroelectric was demonstrated are presented. Attempts to use the ferroelectric polarization to influence the behavior of supported catalytic metals will also be described. It will be shown that the tendency of the metals to cluster into particles makes it difficult to alter the chemical properties of the metal surface, since it is separated from the ferroelectric by several layers of metal atoms. An alternate approach to increasing the reactivity of ferroelectric surfaces is suggested that involves modifying the surface with atoms that bind strongly to the surface and thus remain atomically dispersed.