Superior Resonant Nanocavities Engineering on the Photonic Crystal-Coupled Emission Platform for the Detection of Femtomolar Iodide and Zeptomolar Cortisol.

Although luminescence spectroscopy has been a promising sensing technology with widespread applications in point-of-care diagnostics and chem-bio detection, it fundamentally suffers from low signal collection efficiency, considerable background noise, poor photostability, and intrinsic omnidirectional emission properties. In this regard, surface plasmon-coupled emission, a versatile plasmon-enhanced detection platform with >50% signal collection efficiency, high directionality, and polarization has previously been explored to amplify the limit of detection of desired analytes. However, high Ohmic loss in metal-dependent plasmonic platforms has remained an inevitable challenge. Here, we develop a hybrid nanocavity interface on a template-free and loss-less photonic crystal-coupled emission (PCCE) platform by the quintessential integration of high refractive index dielectric Nd2O3 "Huygens sources" and sharp-edged silver nanoprisms (NPrs). While efficient forward light scattering characteristics of Nd2O3 nanorods (NRs) present 460-fold emission enhancements in PCCE, the tunable localized plasmon resonances of NPrs display high electromagnetic field confinement at sharp nanotips and protrusions, boosting the enhancements 947-fold. The judicious use of silver NPr (AgNPr) metal-Nd2O3 dielectric hybrid resonances in conjugation with surface-trapped Bloch surface waves of the one-dimensional photonic crystal (1DPhC) displayed unprecedented >1300-fold enhancements. The experimental results are validated by excellent correlations with numerical calculations. The multifold hotspots generated by zero and nonzero nanogaps between the coassembly of NPrs, NRs, and 1DPhCs are used for (i) determination of hyper and hypothyroidism levels through monitoring the concentration of iodide (I-) ions and (ii) single-molecule detection (zeptomolar) of the stress hormone, cortisol, through the synthesized cortisol-rhodamine B conjugate obtained using a simple esterification reaction.