First-principles predictions of HfO$_2$-based ferroelectric superlattices

Abstract: The metastable nature of the ferroelectric phase of HfO$_2$ is a significant impediment to its industrial application as a functional ferroelectric material. In fact, no polar phases exist in the bulk phase diagram of HfO$_2$, which shows a dominant non-polar monoclinic ground state. As a consequence, ferroelectric orthorhombic HfO$_2$ needs to be kinetically stabilized. Here, we propose an alternative approach, demonstrating the feasibility of thermodynamically stabilizing polar HfO$_2$ in superlattices with other simple oxides. Using the composition and stacking direction of the superlattice as design parameters, we obtain heterostructures that can be fully polar, fully antipolar or mixed, with improved thermodynamic stability compared to the orthorhombic polar HfO$_2$ in bulk form. Our results suggest that combining HfO$_2$ with an oxide that does not have a monoclinic ground state generally drives the superlattice away from this non-polar phase, favoring the stability of the ferroelectric structures that minimize the elastic and electrostatic penalties. As such, these diverse and tunable superlattices hold promise for various applications in thin-film ferroelectric devices.