Identifying the Crystalline Orientation of Black Phosphorus Using Angle‐Resolved Polarized Raman Spectroscopy

Abstract An optical anisotropic nature of black phosphorus (BP) is revealed by angle‐resolved polarized Raman spectroscopy (ARPRS), and for the first time, an all‐optical method was realized to identify the crystal orientation of BP sheets, that is, the zigzag and armchair directions. We found that Raman intensities of A g 1 , B 2g , and A g 2 modes of BP not only depend on the polarization angle α, but also relate to the sample rotation angle θ. Furthermore, their intensities reach the local maximum or minimum values when the crystalline orientation is along with the polarization direction of scattered light (e s ). Combining with the angle‐resolved conductance, it is confirmed that A g 2 mode intensity achieves a relative larger (or smaller) local maximum under parallel polarization configuration when armchair (or zigzag) direction is parallel to e s . Therefore, ARPRS can be used as a rapid, precise, and nondestructive method to identify the crystalline orientation of BP layers.