We reported the fabrication of a substrate with cavity-nanorod and decorated by Ag-nanoplates (C-NR@Ag). The cavities on the substrate are formed by metal assistant chemical etching (MACE), and Ag-nanoplates in cavities by galvanic cell enhance the SERS performance effectively. Analytes in solution are adsorbed on Ag-nanoplates and located in hot spots, which enhance the SERS performance effectively. The enhancement factor (EF) of the Ag-nanoplates decorated on nanorod cavities is calculated to be 3.6 × 106, and about 3 folds than that on nanorod. The C-NR@Ag substrate is able to detect polychlorinated biphenyls (PCBs) with the lower limit of detection at 1.0 ? 10−12 M. Additionally, due to the semi-volatile of PCB-77, the lower limit of detection of C-NR@Ag substrate for PCB-77 was 1.0 ?10-11 M by non-contact collection method. These results present a novel approach towards enhancing SERS performance and facilitating the rapid detection of PCB-77.

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