Factors Favoring Ferroelectricity in Hafnia: A First-Principles Computational Study

The surprising ferroelectricity displayed by hafnia thin films has been attributed to a metastable polar orthorhombic (<i>Pca</i>2₁) phase. Nevertheless, the conditions under which this (or another competing) ferroelectric phase may be stabilized remain unresolved. It has been hypothesized that a variety of factors, including strain, grain size, electric field, impurities and dopants, may contribute to the observed ferroelectricity. Here, we use first-principles computations to examine the influence of mechanical and electrical boundary conditions (i.e., strain and electric field) on the relative stability of a variety of relevant nonpolar and polar phases of hafnia. We find that although strain or electric field, independently, do not lead to a ferroelectric phase, the combined influence of in-plane equibiaxial deformation and electric field results in the emergence of the polar <i>Pca</i>2₁ structure as the equilibrium phase. The results provide insights for better controlling the ferroelectric characteristics of hafnia thin films by adjusting the growth conditions and electrical history