Origin of the Critical Thickness in Improper Ferroelectric Thin Films

Improper ferroelectrics are expected to be more robust than conventional ferroelectrics against depolarizing field effects and to exhibit a much-desired absence of critical thickness. Recent studies, however, revealed the loss of ferroelectric response in epitaxial improper ferroelectric thin films. Here, we investigate improper ferroelectric hexagonal YMnO₃ thin films and find that the polarization suppression, and hence functionality, in the thinner films is due to oxygen off-stoichiometry. We demonstrate that oxygen vacancies form on the film surfaces to provide the necessary charge to screen the large internal electric field resulting from the positively charged YMnO₃ surface layers. Additionally, we show that by modifying the oxygen concentration of the films, the phase transition temperatures can be substantially tuned. We anticipate that our findings are also valid for other ferroelectric oxide films and emphasize the importance of controlling the oxygen content and cation oxidation states in ferroelectrics for their successful integration in nanoscale applications.