Uncovering Antipolar Ordering and Pressure-Tunable Phases in Hexagonal LaN

TL;DR

This study predicts antipolar and polar phase instabilities in hexagonal LaN using first-principles calculations, revealing pressure-tunable phase competition and potential polarization switching pathways.

Contribution

It uncovers antipolar instability and phase competition in LaN, demonstrating pressure-dependent tunability between polar and antipolar phases with potential for polarization switching.

Findings

Antipolar instability identified in hexagonal LaN.

Pressure decreases energy barrier between phases.

Hexagonal phases become less stable at higher pressures.

Abstract

We predict an antipolar instability in hexagonal LaN using first-principles density functional theory. Starting from a nonpolar hexagonal phase, we identify competing polar and antipolar zone-center phonon instabilities. Condensation of the polar and antipolar modes stabilizes, respectively, dynamically stable wurtzite (WZ) phase and an hexagonal antipolar (AP) phase which is characterized by alternating local polarization and zero net macroscopic polarization within the unit cell. At ambient conditions, the AP phase is metastable with respect to the WZ phase, and a finite energy barrier exists between these phases, suggesting a possible polarization-switching pathway via the AP intermediate state. The energy barrier between the WZ and AP phases decreases with increasing pressure, indicating enhanced tunability between polar and antipolar states. The sublattice polarization increases with pressure in the AP phase, while it decreases in the WZ phase. We further find that, with increasing pressure, the rock-salt and tetragonal phases of LaN become more stable than the hexagonal phases (AP and WZ). Consequently, the realization of the AP phase is more favorable in the low-pressure regime, where hexagonal phases remain energetically competitive. These results demonstrate pressure-driven competition between polar and antipolar phases in LaN and point toward antiferroelectric-like behavior in this binary nitride system.