In this study, we have developed a plasmonic hybrid heterostructure integrating two elements: Two-dimensional (2D) reduced graphene oxide–gold nanostars composite (rGO-GNS), and gold nanostars (GNS) substrate. By harnessing the unique plasmonic properties of rGO in chemical enhancement and that of GNS in electromagnetic enhancement, the hybrid heterostructure offers synergistic enhancement effects that enable ultra-low sensitivity and accurate identification and analysis of trace quantities of target substances. It is noteworthy that the high-density hotspots generated by strong plasmonic coupling of rGO-GNS and GNS results in ultra-high surface-enhanced Raman spectroscopy (SERS) enhancement compared to individual substrate either GNS or rGO-GNS substrate. Moreover, the uniformity and reproducibility of the GNS@rGO-GNS substrate were studied by using thiophenol (TP) as a model analyte, which indicates that the SERS sensor exhibited superior signal reproducibility with an RSD value 5% and long-term stability with a minimal signal loss after 30 days. To demonstrate a potential application of our SERS substrate, SERS detection of the pesticide thiram in river water was realized with a limit of detection (LOD) up to 50 pM, showing the potential for new opportunities for efficient chemical and biological sensing applications.
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