nl0c01784_si_001.pdf (42.64 MB)
Reversible Pressure-Induced Partial Phase Transition in Few-Layer Black Phosphorus
journal contribution
posted on 2020-07-13, 19:34 authored by Anirban Kundu, Damien Tristant, Natalya Sheremetyeva, Anthony Yoshimura, Abraao Torres Dias, Kiran Shankar Hazra, Vincent Meunier, Pascal PuechThe experimental
identification of structural transitions in layered
black phosphorus (BP) under mechanical stress is essential to extend
its application in microelectromechanical (MEMS) devices under harsh
conditions. High-pressure Raman spectroscopic analysis of BP flakes
suggests a transition pressure at ∼4.2 GPa, where the BP’s
crystal structure progressively transforms from an orthorhombic to
a rhombohedral symmetry (blue phosphorus, bP). The phase transition
has been identified by observing a transition from blueshift to redshift
of the in-plane characteristic Raman modes (B2g and Ag2) with increasing
pressure. Recovery of the vibrational frequencies for all three characteristic
Raman modes confirms the reversibility of the structural phase transition.
First-principles calculations provide insight into the behavior of
the Raman modes of BP under high pressure and reveal the mechanism
responsible for the partial phase transition from BP to bP, corresponding
to a metastable equilibrium state where both phases coexist.