Phonon Signatures of Near-Room-Temperature Phase Transition in Quasi-One-Dimensional Bi4I4 Topological van der Waals Material

TL;DR

This study uses polarization-resolved Raman spectroscopy and DFT calculations to detect a subtle stacking-driven structural transition in Bi4I4, revealing phonon signatures of topological phase change near room temperature.

Contribution

It demonstrates that Raman spectroscopy can identify stacking-induced topological phase transitions without a change in space group in Bi4I4.

Findings

Phonon modes show abrupt, hysteretic shifts across the transition.

DFT confirms phonon sensitivity to stacking-dependent force constants.

Raman spectroscopy detects subtle structural changes linked to topological phases.

Abstract

The quasi-one-dimensional material Bi4I4 hosts two crystallographically similar polymorphs that realize distinct topological insulating phases separated by a first-order structural transition near room temperature. This transition occurs without a change in space group, arising instead from a subtle rearrangement of chain stacking registry. Polarization-resolved Raman spectroscopy directly resolves this structural-topological phase transition through abrupt, hysteretic modifications of the phonon spectrum. Angle-dependent measurements establish the symmetry of the dominant Raman-active modes and require a complex Raman tensor formalism to account for absorption-induced phase effects. Across the transition, selected phonon modes exhibit discontinuous, reversible shifts in frequency, linewidth, and relative intensity despite the absence of a space-group change. Density functional theory calculations reproduce the direction of the observed phonon renormalizations and confirm their sensitivity to stacking-dependent force constants. These results demonstrate that polarization-resolved Raman spectroscopy can detect subtle stacking-driven structural rearrangements that underlie topological band character, even when global crystallographic symmetry remains unchanged. The obtained results provide valuable insights into the interplay among lattice dynamics, structural distortions, and topological properties in this class of low-dimensional materials, with strong potential for unique functionalities.