Anticorrelation of Photoluminescence from Gold Nanoparticle Dimers with Hot-Spot Intensity

Bulk gold shows photoluminescence (PL) with a negligible quantum yield of ∼10-10, which can be increased by orders of magnitude in the case of gold nanoparticles. This bears huge potential to use noble metal nanoparticles as fluorescent and unbleachable stains in bioimaging or for optical data storage. Commonly, the enhancement of the PL yield is attributed to nanoparticle plasmons, specifically to the enhancements of scattering or absorption cross sections. Tuning the shape or geometry of gold nanostructures (e.g., via reducing the distance between two nanoparticles) allows for redshifting both the scattering and the PL spectra. However, while the scattering cross section increases with a plasmonic redshift, the PL yield decreases, indicating that the common simple picture of a plasmonically boosted gold luminescence needs more detailed consideration. In particular, precise experiments as well as numerical simulations are required. Hence, we systematically varied the distance between the tips of two gold bipyramids on the nanometer scale using AFM manipulation and recorded the PL and the scattering spectra for each separation. We find that the PL intensity decreases as the interparticle coupling increases. This anticorrelation is explained by a theoretical model where both the gold-intrinsic d-band hole recombination probabilities as well as the field strength inside the nanostructure are considered. The scattering cross section or the field strength in the hot-spot between the tips of the bipyramids are not relevant for the PL intensity. Besides, we not only observe PL supported by dipolar plasmon resonances, but also measure and simulate PL supported by higher order plasmonic modes.