Plasmon-Free Surface-Enhanced Raman Spectroscopy Using Metallic 2D Materials.

Two dimensional (2D) materials-based plasmon-free surface-enhanced Raman scattering (SERS) is an emerging field in nondestructive analysis. However, impeded by the low density of state (DOS), an inferior detection sensitivity is frequently encountered due to the low enhancement factor of most 2D materials. Metallic transition-metal dichalcogenides (TMDs) could be ideal plasmon-free SERS substrates because of their abundant DOS near the Fermi level. However, the absence of controllable synthesis of metallic 2D TMDs has hindered their study as SERS substrates. Here, we realize controllable synthesis of ultrathin metallic 2D niobium disulfide (NbS2) (<2.5 nm) with large domain size (>160 μm). We have explored the SERS performance of as-obtained NbS2, which shows a detection limit down to 10-14 mol·L-1. The enhancement mechanism was studied in depth by density functional theory, which suggested a strong correlation between the SERS performance and DOS near the Fermi level. NbS2 features the most abundant DOS and strongest binding energy with probe molecules as compared with other 2D materials such as graphene, 1T-phase MoS2, and 2H-phase MoS2. The large DOS increases the intermolecular charge transfer probability and thus induces prominent Raman enhancement. To extend the results to practical applications, the resulting NbS2-based plasmon-free SERS substrates were applied for distinguishing different types of red wines.