Origin of ferroelectricity and multiferroicity in binary oxide thin films

TL;DR

This paper extends the Landau-Ginzburg-Devonshire theory to explain the origin of ferroelectricity and multiferroicity in binary oxide thin films, highlighting the role of oxygen vacancies and surface effects in their physical properties.

Contribution

It applies a generalized LGD model to a broad class of binary oxides, demonstrating their potential as multiferroics with tunable properties for nanoelectronics.

Findings

Binary oxide thin films can be multiferroic due to oxygen vacancies.

Film properties depend on vacancy concentration, thickness, and treatment.

Theoretical predictions align with observed ferroelectric and magnetic behaviors.

Abstract

The observation of ferroelectric, ferromagnetic and ferroelastic phases in thin films of binary oxides attract the broad interest of scientists and engineers. However, the theoretical consideration of observed behaviour physical nature was performed mainly for HfO2 thin films from the first principles, and in the framework of Landau-Ginzburg-Devonshire (LGD) phenomenological approach with a special attention to the role of oxygen vacancies in both cases. Allowing for generality of the LGD theory we applied it to the group of binary oxides in this work. The calculations have been performed in 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" entire the depth of an ultra-thin film. We calculated the dependence of the film polarization on the applied voltage for room temperature and different film thickness. Since the many films of binary oxide are ferroelectric and ferromagnetic due to the same oxygen vacancies, they can be multiferroics. Performed calculations have shown that thin films of binary oxides can be considered as a new wide class of multiferroics with broad spectra of physical properties useful for application in nanoelectronics and nanotechnology. The properties can be controlled by the choice of oxygen vacancies concentration, film thickness and special technological treatment, such as annealing.