Anomalous Phonon Modes in Black Phosphorus Revealed by Resonant Raman Scattering.

Black phosphorus (BP), a layered material with puckered crystalline structure in each layer, has drawn intense interest due to its unique optical and electronic properties. In particular, the intricate Raman scattering effect in BP is intriguing and provides a platform for researchers to probe the physical properties of BP in depth. Here we report the first observation of anomalous modes with the frequency in the range of 100-900 cm-1 in BP due to the resonant Raman effect. The origin and assignment of the anomalous modes are discussed based on the excitation energy- and angle-dependent Raman measurements. Density functional theory (DFT) calculated electronic band structure is used to support our understanding. The newly observed phonon modes could serve as a unique probe for the fine electronic structures and the exciton-phonon couplings, which promote a better understanding of BP for potential nanoelectronic and nanophotonic applications in the future.