Rationally Designed Graphene/Bilayer Silver/Cu Hybrid Structure with Improved Sensitivity and Stability for Highly Efficient SERS Sensing.

A simple and cost-effective strategy was rationally designed to fabricate a special sandwich structure consisting of graphene, bilayer silver, and a copper plate, which was used as a surface-enhanced Raman scattering (SERS) substrate for highly efficient SERS sensing and detection of trace molecules. Silver dendrite (AgD) nanostructures were subsequently grown on a silver nanosphere (AgNS)/Cu surface to form a bilayer silver/Cu structure, which showed a 1.5-fold Raman enhancement compared to that of the AgNS/Cu substrate. After depositing graphene on the bilayer silver/Cu substrate to obtain a sandwich structure, a higher SERS enhancement and better durability were enabled. The SERS performances, measured by a portable Raman instrument, showed that the optimized sandwich structure substrate exhibited high SERS sensitivity to crystal violet (CV) and rhodamine 6G (R6G) with low limit of detection of 10 and 10 M, respectively. Such a sandwich-structured substrate exhibited good reproducibility across the entire detection areas with an average relative standard deviation less than 5.9%, which permits its reliable quantitative detection of CV and R6G molecules. In addition, graphene both effectively improved the SERS performances and protected Ag nanocrystals from oxidation, which endowed the sandwich structure a long-term stability with deviation of characteristic peaks' intensity lower than 3.6% after 25 days. This study indicates that the graphene/bilayer silver/Cu sandwich structure as a SERS substrate has a great potential in detecting environmental pollutants.