Ultra-clean ternary Au/Ag/AgCl nanoclusters favoring cryogenic temperature-boosted broadband SERS ultrasensitive detection

Abstract

Exploring multifunctional surface-enhanced Raman scattering (SERS) substrates with high sensitivity, broadband response property and reliable practicability should be required for ultrasensitive molecular detection in complex environments, which is heavily dependent on the photo-induced charge transfer (PICT) efficiency realized on the desirable nano-architectures. Herein, we introduce ultra-clean ternary Au/Ag/AgCl nanoclusters (NCs) with broadband resonance crossing the visible light to near-infrared region created by one step laser irradiation of mixed metal ion solution. Interestingly, the surface defects and interaction among these unique cluster-like ternary nanostructures would be further enhanced by thermal annealing treatment at 300°C, providing higher broadband SERS activities than the reference ternary nanoparticles under 457, 532, 633, 785, and 1064 nm wavelengths excitation. More importantly, the further promoted SERS activities of the resultant Au/Ag/AgCl NCs with achievable ∼5-fold enhancement than the initial one can be conventionally realized by simplistically declining the temperature from normal 20°C to cryogenic condition at about -196°C, due to the lower temperature-suppressed non-radiative recombination of lattice thermal phonons and photogenerated electrons. The cryogenic temperature-boosted SERS of the resultant Au/Ag/AgCl NCs enables the limit of detection (LOD) of folic acid (FA) biomolecules to be achieved as low as 10−12 M, which is obviously better than that of 10−9 M at room temperature condition. Overall, the smart Au/Ag/AgCl NCs-based broadband SERS sensor provides a new avenue for ultrasensitive biomolecular monitoring at cryogenic condition.