Enhanced Raman Scattering on In-Plane Anisotropic Layered Materials

Surface-enhanced Raman scattering (SERS) on two-dimensional (2D) layered materials has provided a unique platform to study the chemical mechanism (CM) of the enhancement due to its natural separation from electromagnetic enhancement. The CM stems from the charge interactions between the substrate and molecules. Despite the extensive studies of the energy alignment between 2D materials and molecules, an understanding of how the electronic properties of the substrate are explicitly involved in the charge interaction is still unclear. Lately, a new group of 2D layered materials with anisotropic structures, including orthorhombic black phosphorus (BP) and triclinic rhenium disulfide (ReS₂), has attracted great interest due to their unique anisotropic electrical and optical properties. Herein, we report a unique anisotropic Raman enhancement on few-layered BP and ReS₂ using copper phthalocyanine (CuPc) molecules as a Raman probe, which is absent on isotropic graphene and h-BN. According to detailed Raman tensor analysis and density functional theory calculations, anisotropic charge interactions between the 2D materials and molecules are responsible for the angular dependence of the Raman enhancement. Our findings not only provide new insights into the CM process in SERS, but also open up new avenues for the exploration and application of the electronic properties of anisotropic 2D layered materials.