Hafnia HfO$_2$ is a Proper Ferroelectric

TL;DR

This paper demonstrates that hafnia is a proper ferroelectric with a shallow double well involving a soft polar mode, confirmed through symmetry analysis and density functional theory calculations, showing its ferroelectric properties are intrinsic and strain-independent.

Contribution

It provides a detailed theoretical analysis establishing hafnia as a proper ferroelectric with a specific polar phase and clarifies that strain is not necessary for its ferroelectric switching behavior.

Findings

Hafnia exhibits a shallow double well with a single soft polar mode.

The ferroelectric phase Pca2_1 is most consistent with experimental observations.

Ferroelectric properties are intrinsic and do not require strain or mode coupling.

Abstract

We clarify the nature of hafnia as a proper ferroelectric and show that there is a shallow double well involving a single soft polar mode as in well-known classic ferroelectrics. Using symmetry analysis, density-functional theory (DFT) structural optimizations with and without epitaxial strain, and density functional perturbation theory (DFPT), we examine several important possible hafnia structures derived ultimately from the cubic fluorite structure, including baddeleyite ($P2_{1}/c$) tetragonal antiferroelectric $P4_{2}nmc$, $Pbca$ (nonpolar and brookite), ferroelectric rhombohedral ($R3m$ and $R3$), $Pmn2_{1}$, and $Pca2_{1}$ structures. The latter is considered to be the most likely ferroelectric phase seen experimentally, and has an antiferroelectric parent with space group $Pbcn$, with a single unstable polar mode and a shallow double well with a well depth of 24 meV/atom. Strain is not required for switching or other ferroelectric properties, nor is coupling of the soft-mode with any other modes within the ferroelectric $Pca2_{1}$, $Pmn2_{1}$, $R3m$ or $R3$ phases.