Raman anomalies as signatures of pressure induced electronic topological and structural transitions in black phosphorus: Experiments and Theory

TL;DR

This study combines high-pressure Raman experiments and first-principles calculations to identify signatures of electronic topological and structural transitions in black phosphorus under pressure.

Contribution

It provides new insights into pressure-induced electronic and structural phase transitions in black phosphorus through combined experimental and theoretical analysis.

Findings

Raman mode linewidths show anomalies at 1.1 GPa indicating electronic transition.

Frequency anomalies in Raman modes occur at 7.4 GPa during structural phase change.

New Raman modes exhibit pressure-induced softening in the rhombohedral phase.

Abstract

We report high pressure Raman experiments of Black phosphorus up to 24 GPa. The line widths of first order Raman modes A$^1_g$, B$_{2g}$ and A$^2_g$ of the orthorhombic phase show a minimum at 1.1 GPa. Our first-principles density functional analysis reveals that this is associated with the anomalies in electron-phonon coupling at the semiconductor to topological insulator transition through inversion of valence and conduction bands marking a change from trivial to nontrivial electronic topology. The frequencies of B$_{2g}$ and A$^2_g$ modes become anomalous in the rhombohedral phase at 7.4 GPa, and new modes appearing in the rhombohedral phase show anomalous softening with pressure. This is shown to originate from unusual structural evolution of black phosphorous with pressure, based on first-principles theoretical analysis.