Active substrates are crucial for surface-enhanced Raman scattering (SERS). Among these substrates, large uniform area arrayed nanoporous silver thin films have been developed as active substrates. Arrayed nanoporous silver thin films with unique anisotropic morphologies and nanoporous structures can be fabricated onto the nanoporous anodic aluminum oxide (AAO) of controlled pore size and interspacing by precisely tuning the sputtering parameters. These thin films preserve locally enhanced electromagnetic fields by exciting the surface plasmon resonance, which is beneficial for SERS. In this study, nanoporous silver thin films were transferred into polymethylmethacrylate (PMMA) and polydimethylsiloxane (PDMS) substrates using our recently invented template-assisted sol-gel phase inverse-imprinting process to form two different nanopore thin films. The as-formed Ag nanoporous thin films on PMMA and PDMS exhibited intensively enhanced SERS signals using Rhodamine 6G (R6G) as the model molecule. The two nanopore thin films exhibited opposite pore size-dependent SERS tendencies, which were elucidated by the different enhancement tendencies of the electric field around pores of different diameters. In particular, the Ag nanoporous thin film on PMMA exhibited an R6G detection limit of as low as 10-6 mol L-1, and the SERS enhancement factor (EF) was more than 106. The low detection limit and large EF demonstrated the high sensitivity of the as-prepared SERS substrates for label-free detection of biomolecules. Compared with conventional smooth films, this nanopore structure can facilitate future application in biomolecular sensors, which allows the detection of single molecules via an electronic readout without requirement for amplification or labels.
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