Cascaded microsphere-coupled surface-enhanced Raman spectroscopy (CMS-SERS) for ultrasensitive trace-detection

Surface-enhanced Raman spectroscopy (SERS) has been widely investigated and employed as a powerful optical analytical technique providing fingerprint vibrational information of molecules with high sensitivity and resolution. In addition to metallic nanostructure, dielectric micro-/nano-structures with extraordinary optical manipulation properties have demonstrated capability in enhanced Raman scattering with ultralow energy losses. Here we report a facile cascaded structure composed of a large microsphere (LMS) and a small microsphere array with Ag nanoparticles as a novel hybrid SERS substrate, for the first time. The cascaded microsphere-coupled SERS substrate provides a platform to increase the molecular concentration, boost the intensity of localized excitation light, and direct the far-field emission, for giant Raman enhancement. It demonstrates the maximum enhancement factor of Raman intensity greater than 108 for the limit of detection down to 10−11 M of 4-nitrothiphenol molecules in aqueous solution. The present work inspires a novel strategy to fabricate cascaded dielectric/metallic micro-/nano-structures superior to traditional SERS substrates towards practical applications in cost-effective and ultrahigh-sensitive trace-detection.