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.

Surface‐enhanced Raman spectroscopy (SERS) is a powerful tool for nondestructive and ultrasensitive optical trace‐detection. However, the sophisticated fabrication processes and performance degradation on flexible substrates block SERS for practical uses. Here, we report a facile flexible microsphere‐coupled SERS (McSERS) substrate composed of a dielectric microsphere cavity array (MCA) and random gold nanoparticles (AuNPs) capping on a polydimethylsiloxane (PDMS) film (MCA/AuNPs/PDMS) for giant Raman enhancement. The random distribution of AuNPs provides a hydrophilic surface against to the coffee‐ring effect for uniform localized surface plasmon resonance (LSPR) response. The MCA capped on the AuNPs boosts the Raman intensity via the multiple optical manipulation processes, in which the photonic nanojet (PNJ) confines the excitation intensity near the AuNPs, whispering‐gallery mode (WGM) facilitates the energy transfer from microsphere cavities to AuNP gaps for LSPR boosting, and directional antenna effect converts near‐field Raman signals into far‐field with a small divergence. Therefore, the Raman scattering is dramatically improved with the enhancement factor (EF) to 107 for the limit of detection (LoD) of 4‐nitrobenzenethiol (4‐NBT) molecules down to 0.1 nM, two orders of magnitude higher via MCA coupling. Moreover, the flexible McSERS substrate exhibits outstanding durability and compatibility as an ultrasensitive Raman test strip, by which the thiram concentration is detectable down to 2.42 ng/cm2 on apple peels. The present work provides a facile strategy to fabricate SERS substrates with high flexibility for optical trace‐detection in real‐world applications.

Increasing upconversion luminescence (UCL) to overcome the intrinsically low conversion efficiency of upconversion nanoparticles (UCNPs) poses a fundamental challenge. Photonic nanostructures are the efficient approaches for UCL enhancement by tailoring the local electromagnetic fields. Unfortunately, such nanostructures are sensitive to environmental conditions, and the regulation strength is varied in flexible applications. Here, we report giant UCL enhancement from a flexible UCNP-embedded film coupled with a microsphere photonic superlens (MPS), by which the enhancement ratio of UCL is over 10 4 -fold under 808 nm excitation down to 0.72 mW. The enhancement pathways of MPS-enhanced UCL are attributed to Mie-resonant nanofocusing for high excitationphoton density, optical whispering-gallery modes (WGMs) for fast radiative decay, and the directional antenna effect for far-field emission confinement. The contribution of optical resonance in the MPS to suppressing the phonon-induced nonradiative transition and thermal quenching is experimentally validated. The UCL quantum yield is therefore improved by 3-fold to 4.20% under 120 mW/cm 2 near-infrared excitation, consistent with the enhancement ratio via the Purcell effect of WGMs. Furthermore, the MPS demonstrates the robust optical regulation capability toward flexible applications, opening up new opportunities for facilitating multiphoton upconversion in wearable optoelectrical devices for nanoimaging, biosensing, and energy conversion in the future.

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