Ultrasensitive Molecular Fingerprint Retrieval Using Strongly Detuned Overcoupled Plasmonic Nanoantennas

Tailoring light-matter interactions via plasmonic nanoantennas (PNAs) has emerged as a breakthrough technology for spectroscopic applications. The detuning between molecular vibrations and plasmonic resonances, as a fundamental and inevitable optical phenomenon in light-matter interactions, reduces the interaction efficiency, resulting in a weak molecule sensing signal at the strong detuning state. Here, it is demonstrated that the low interaction efficiency from detuning can be tackled by overcoupled PNAs (OC-PNAs) with a high ratio of the radiative to intrinsic loss rates, which can be used for ultrasensitive spectroscopy at strong plasmonic-molecular detuning. In OC-PNAs, the ultrasensitive molecule signals are achieved within a wavelength detuning range of 248 cm^-1 , which is 173 cm^-1 wider than previous works. Meanwhile, the OC-PNAs are immune to the distortion of molecular signals and maintain a lineshape consistent with the molecular signature fingerprint. This strategy allows a single device to enhance and capture the full and complex fingerprint vibrations in the mid-infrared range. In the proof-of-concept demonstration, 13 kinds of molecules with some vibration fingerprints strongly detuning by the OC-PNAs are identified with 100% accuracy with the assistance of machine-learning algorithms. This work gains new insights into detuning-state nanophotonics for potential applications including spectroscopy and sensors.