Second-Order Raman Scattering in Exfoliated Black Phosphorus

TL;DR

This study identifies and characterizes four second-order Raman modes in exfoliated black phosphorus, revealing their defect-activation, anisotropic phonon involvement, and sensitivity to disorder, advancing understanding of its vibrational properties.

Contribution

The paper reports the discovery of four new second-order Raman modes in black phosphorus and elucidates their defect-activated nature and anisotropic phonon interactions through experiments and ab initio simulations.

Findings

Four new second-order Raman modes identified in black phosphorus.

Modes are defect-activated and involve high-momentum phonons.

Modes show sensitivity to disorder and sample conditions.

Abstract

Second-order Raman scattering has been extensively studied in carbon-based nanomaterials, \emph{e.g.} nanotube and graphene, because it activates normally forbidden Raman modes that are sensitive to crystal disorder, such as defects, dopants, strain, etc. The sp$^2$-hybridized carbon systems are, however, the exception among most nanomaterials, where first-order Raman processes usually dominate. Here we report the identification of four second-order Raman modes, named $D_1$, $D_1'$, $D_2$ and $D_2'$, in exfoliated black phosphorus (P(black)), an elemental direct-gap semiconductor exhibiting strong mechanical and electronic anisotropies. Located in close proximity to the $A^1_g$ and $A^2_g$ modes, these new modes dominate at an excitation wavelength of 633 nm. Their evolutions as a function of sample thickness, excitation wavelength, and defect density indicate that they are defect-activated and involve high-momentum phonons in a doubly-resonant Raman process. \emph{Ab initio} simulations of a monolayer reveal that the $D'$ and $D$ modes occur through intravalley scatterings with split contributions in the armchair and zigzag directions, respectively. The high sensitivity of these $D$ modes to disorder helps explaining several discrepancies found in the literature.