Raman spectroscopy in black phosphorus

Abstract

In this article, we review the current status of Raman spectroscopy in orthorhombic black phosphorus (BP) (for simplicity, henceforth, referred to as BP). BP is a layered semiconductor crystal that recently regained interest because it can be exfoliated down to the single layer, thus exhibiting 2-D properties. First, we briefly review the crystalline structure and the phonon dispersion relations in BP. Then, the symmetries of the Raman-active modes are discussed in the light of group theory, and the scattering configurations for observing the different phonon modes are presented. Polarized Raman spectroscopy results are discussed and reveal unusual angular dependence features, which can be ascribed to the linear dichroism and to the complex nature of the electron-phonon matrix elements. Edge phonon effects originated from rearrangements of the atomic terminations are also discussed. Subsequently, Raman modes that emerge from interlayer interaction and that are only visible in the few-layer regime are presented and discussed. Finally, we outline new perspectives to BP Raman spectroscopy in directions that remain partially or totally unexplored and that can provide potentially important outcomes to problems such as defects, oxidation, doping, strain, stacking order and other BP-like 2-D materials.

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

“…Ribeiro and co‐workers described the Raman spectroscopy in black phosphorus. They reviewed the current status of Raman spectroscopy in orthorhombic black phosphorus, a layered semiconductor crystal that recently regained interest because it can be exfoliated down to the single layer, thus exhibiting 2D properties . Son and co‐workers presented a Raman study on the effects of an annealing atmosphere on patterned graphene.…”

“…Jorio presented a dedication to the life‐long contributions of Mildred S. Dresselhaus (1930–2017) in the same special issue of JRS highlighting her contributions to our understanding of graphite, graphite intercalated compounds, graphite ion‐implantation, graphite fibers, fullerenes, carbon nanotubes, and two‐dimensional systems, starting from graphene . Other reviews in the special issue on graphene and related 2D materials, previously described above, were the following: Beams on Tip‐enhanced Raman scattering of graphene ; Faugeras and co‐workers on Raman scattering of graphene‐based systems in high magnetic fields ; Bendiab et al on Unravelling external perturbation effects on the optical phonon response of graphene ; Lee and Cheong on Resonance Raman effects in transition metal dichalcogenides ; Machon et al on Raman scattering studies of graphene under high pressure ; and Ribeiro and co‐workers on the Raman spectroscopy in black phosphorus . Huang and colleauges provided a conference report from the 5th International Taiwan Symposium on Raman Spectroscopy (2017) and Taiwan Association of Raman Spectroscopy Summer Camp .…”

“…They reviewed the current status of Raman spectroscopy in orthorhombic black phosphorus, a layered semiconductor crystal that recently regained interest because it can be exfoliated down to the single layer, thus exhibiting 2D properties. [101] Son and co-workers presented a Raman study on the effects of an annealing atmosphere on patterned graphene. They conclude that graphene in microscopic devices should be treated differently from the as-grown graphene.…”

Strain engineering of the lattice vibration modes in monolayer black phosphorus

“…Moreover, the strain engineering is also a significant mechanism to tailor and modulate the physical properties of 2D materials Therefore, it is important to identify the strain‐induced deformation patterns and clarify the relationship between strain and resulted variations of lattice bond parameters in BP. In this regard, the Raman technique offers an effective and nondestructive approach to address the proposed issues . Recently, Fei et al .…”

“…In this regard, the Raman technique offers an effective and nondestructive approach to address the proposed issues. [12,13] Recently, Fei et al [14] reported the lattice vibrational modes and corresponding Raman spectra of strained monolayer BP by first-principles simulations.…”