Angular resolved ultra-low frequency Raman spectroscopy of few-layer black phosphorous

Few-layer black phosphorus (FLBP) exhibits valuable mechanical, optical, and electronic properties for potential applications in nanodevices, ranging from insulators to superconductors. In particular, their band structure and optical properties are closely related to layer numbers, stacking sequences, and twist angles. However, the mechanism behind these factors is not fully understood, as it is quite difficult to obtain stacking details using non-destructive probes. This article provides direct experimental evidence of the weak interlayer van der Waals (vdW) interaction of FLBP using a state-of-the-art, angular resolved, ultra-low frequency Raman spectroscopy system. A modified linear-chain model is presented to evaluate the layer number dependence on the extremely low-frequency breathing modes (Ag3 and Ag4). The polarization analysis illustrates that most bi-layer BP samples prefer the AB stacking sequence. Furthermore, the stacking angle of bi-layer BP was assigned based on its minimum intensity of Ag3 and Ag4 modes. This investigation on angular resolved extremely low-frequency Raman spectra sheds light on a new approach for analyzing the stacking details of FLBP, which is of great significance for developing novel FLBP-based nanodevices.