Origin of Ferroelectricity and Multiferroicity in Binary Oxide Thin Films.

The observation of ferroelectric, ferromagnetic, and ferroelastic phases in thin films of binary oxides attracts the broad interest of scientists and engineers. However, the theoretical consideration of the physical nature of the observed behavior was performed mainly for HfO thin films from the first principles, and in the framework of Landau-Ginzburg-Devonshire (LGD) phenomenological approach with special attention to the role of oxygen vacancies in both cases. Allowing for the generality of the LGD theory, we applied it to the group of binary oxides in this work. The calculations have been performed based on the assumption that oxygen vacancies, as elastic dipoles, can be partially transformed into electric dipoles due to the defect site-induced and/or surface-induced inversion symmetry breaking (via, e.g., piezoelectric effect), and can "migrate" throughout the depth of an ultrathin film. Since many films of binary oxide are ferroelectric and ferromagnetic due to the oxygen vacancies, they can be multiferroics. Performed calculations have shown that thin films of binary oxides can be considered as new multiferroics with physical properties useful for broad spectra of applications in nanoelectronics and nanotechnology. The properties can be controlled by the choice of oxygen vacancy concentration, film thickness, and special technological treatment, such as annealing.