Bridging the Nanogap with Light: Continuous Tuning of Plasmon Coupling between Gold Nanoparticles

The control of nanogaps lies at the heart of plasmonics for nanoassemblies. The plasmon coupling sensitively depends on the size and the shape of the nanogaps between nanoparticles, permitting fine-tuning of the resonance wavelength and near-field enhancement at the gap. Previously reported methods of molecular or lithographic control of the gap distance are limited to producing discrete values and encounter difficulty in achieving subnanometer gap distances. For these reasons, the study of the plasmon coupling for varying degrees of interaction remains a challenge. Here, we report that by using light, the interparticle distance for gold nanoparticle (AuNP) dimers can be continuously tuned from a few nanometers to negative values (i.e., merged particles). Accordingly, the plasmon coupling between the AuNPs transitions from the classical electromagnetic regime to the contact regime via the nonlocal and quantum regimes in the subnanometer gap region. We find that photooxidative desorption of alkanedithiol linkers induced by UV irradiation causes the two AuNPs in a dimer to approach each other and eventually merge. Light-driven control of the interparticle distance offers a novel means of exploring the fundamental nature of plasmon coupling as well as the possibility of fabricating nanoassemblies with any desired gap distance in a spatially controlled manner.