Spectral Properties of Individual DNA-Hosted Silver Nanoclusters at Low Temperatures

We report on the first single emitter fluorescence spectra of DNA-stabilized silver clusters (Ag:DNAs) at ambient and cryogenic temperatures. While Ag:DNAs have received much attention recently due to their sequence-tunable emission wavelengths, the nature of the optical transitions (molecule-like or collective, cluster-like) is an open question. By removing the ensemble broadening present in previous spectroscopic studies, we probe the line widths Γ and brightness of individual Ag:DNA emitters. A roughly 5-fold increase in brightness from 295 to 1.7 K is accompanied by a factor of 2 decrease in Γ. The symmetric emission line shape, its insensitivity to embedding medium, and the independence of emission wavelength on excitation energy together indicate that the measured Γ represents the homogeneous line width, while the large, ∼100 meV values of Γ suggest rapid dephasing of a collective excited state of the silver cluster.