Symmetry Breaking-Induced Plasmonic Mode Splitting in Coupled Gold-Silver Alloy Nanodisk Array for Ultrasensitive RGB Colorimetric Biosensing.

Abstract

We report the first observation of symmetry breaking-induced mode splitting in coupled gold-silver alloy nanodisk array (ANA). According to the plasmonic hybridization picture, the original localized surface plasmon resonance (LSPR) of individual nanodisk is split into a pair of high and low energy modes when placed in between a superstrate and a substrate. Although well studied in single silver nanoparticles, the high energy mode has been largely suppressed in gold nanoparticles, which nevertheless are more chemically robust and have superior environmental stability. Herein, we show that the high energy mode can be partially restored and precisely engineered to ∼540 nm for silver-rich alloy nanodisk which has excellent environmental stability. However, peak broadening and red-shifting occur due to plasmonic dephasing when the nanodisk diameter increases. We next demonstrate that a far-field coupled ANA fabricated by low-cost nanosphere lithography can fully restore the high energy mode with electric field concentration extended into the superstrate, thereby imparting greater sensitivity to local refractive index changes. The high energy mode at 540 nm is of key importance for color change detection using low-cost RGB cameras/human vision and broadband light sources (e.g., the sun). The index sensitivity of ANA is the highest among existing plasmonic arrays (particles or holes) within a similar resonance wavelength region. We demonstrate colorimetric detection of sub-nanomolar and sub-monolayer biotin-streptavidin surface binding with a smartphone camera and a white light lamp. The high performance yet low-cost fabrication and detection technology could potentially result in affordable point-of-care biosensing technologies.