Origin of Ferroelectricity in Hafnia from Epitaxial Strain

TL;DR

This study uses density functional theory to show how epitaxial strain stabilizes ferroelectric phases in hafnia, explaining its robust ferroelectricity at the nanoscale and identifying specific strain conditions that favor ferroelectricity.

Contribution

It reveals the mechanisms by which epitaxial strain stabilizes ferroelectric phases in hafnia, providing insights into its ferroelectricity origin at the atomic level.

Findings

Epitaxial strain stabilizes ferroelectric phases in hafnia.

Tensile strain favors the I ferroelectric phase.

Strain-induced phase transitions occur at specific strain thresholds.

Abstract

Ferroelectric hafnia is being explored for next generation electronics due to its robust ferroelectricity in nanoscale samples and its compatibility with silicon. However, its ferroelectricity is not understood. Other ferroelectrics usually lose their ferroelectricity for nanoscopic samples and thin films, and the hafnia ground state is non-polar baddeleyite. Here we study hafnia with density functional theory (DFT) under epitaxial strain, and find that strain not only stabilizes the ferroelectric phases, but also leads to unstable modes and a downhill path in energy from the high temperature tetragonal structure. We find that for tensile epitaxial strains corresponding to a square substrate of lattice constant $a_{epi} \geqslant 5.38$ \AA~the ferroelectric \oI is most stable, even more stable than baddeleyite. Furthermore, we find that under tensile epitaxial strain $\eta$ the tetragonal phase will distort to one of the two ferroelectric phases: for $\eta > 1.5$\%, the $\Gamma^{-}_{5}$ mode is unstable and leads to \oII , and at $\eta > 3.75$\% coupling between this mode and the zone boundary M1 mode leads to \oI.