Ag Nanoparticle‐Grafted PAN‐Nanohump Array Films with 3D High‐Density Hot Spots as Flexible and Reliable SERS Substrates

A facile fabrication approach of large-scale flexible films is reported, with one surface side consisting of Ag-nanoparticle (Ag-NP) decorated polyacrylonitrile (PAN) nanohump (denoted as Ag-NPs@PAN-nanohump) arrays. This is achieved via molding PAN films with ordered nanohump arrays on one side and then sputtering much smaller Ag-NPs onto each of the PAN-nanohumps. Surface-enhanced Raman scattering (SERS) activity of the Ag-NPs@PAN-nanohump array films can be improved by curving the flexible PAN film with ordered nanohump arrays during the Ag-sputtering process to increase the density of the Ag-NPs on the sidewalls of the PAN-nanohumps. More 3D hot spots are thus achieved on a large-scale. The Ag-NPs@PAN-nanohump array films show high SERS activity with good Raman signal reproducibility for Rhodamine 6G probe molecules. To trial their practical application, the Ag-NPs@PAN-nanohump array films are employed as SERS substrates for trace detection of trinitrotoluene and a congener of polychlorinated biphenyls. A lower detection limit of 10(-12) m and 10(-5) m can be achieved, respectively. Furthermore, the flexible Ag-NPs@PAN-nanohump array films can also be utilized as swabs to probe traces of methyl parathion on the surface of fruits such as apples. The as-fabricated SERS substrates therefore have promising potential for applications in rapid safety inspection and environmental protection.