Richard Leonelli, Julien Groulx, Richard Martel, Jean-Francis Germain, Michel Côté, Vincent Gosselin, Anne-Laurence Phaneuf-L’Heureux, Félix Antoine Goudreault, Sébastien Francoeur, Alexandre Favron
Second-order Raman scattering has been extensively studied in carbon-based nanomaterials, for example, nanotube and graphene, because it activates normally forbidden Raman modes that are sensitive to crystal disorder, such as defects, dopants, strain, and so forth. The sp2-hybridized carbon systems are, however, the exception among nanomaterials, where first-order Raman processes usually dominate. Here we report the identification of four second-order Raman modes, named D1, D1′, D2 and D2′, in exfoliated black phosphorus (P(black)), an elemental direct-gap semiconductor exhibiting strong mechanical and electronic anisotropies. Located in close proximity to the Ag1 and Ag2 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. 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.