Fine-tuning longitudinal plasmon resonances of nanorods by thermal reshaping in aqueous media

Metallic nanoparticles that support surface plasmons are potential building units for future nanophotonic circuits, metamaterials, high-density optical data storage, etc. Many of these applications require the ability to 'dial-up' the desired plasmonic resonance modes and frequencies with high precision. Here, we demonstrate a thermal reshaping route that can be used to tailor longitudinal plasmon resonance energies of gold nanorods almost continuously from similar to 800 to similar to 560 nm. The longitudinal plasmon resonance wavelength exhibits an exponential decay function of the thermal annealing time at a given temperature. This correlates with the transmission electron microscopy characterization (TEM) which showed that the nanorod aspect ratio decreases exponentially with time, accompanying a gradual shape transformation from rod to sphere. The exponential decay half-time decreases with increasing annealing temperatures, with a value of 1.43 x 10(5) s at 50 degrees C down to 0.02 x 10(5) s at 100 degrees C. Our experimental results show that the shape transformation could be attributed to desorption of silver ions and side facet-binding Ag-Br-CTA ligands, which therefore promote the side growth leading to nanorod fattening. Compared to other synthetic methodologies to tune plasmonics, our thermal reshaping approach presents a straightforward paradigm for precisely tailoring plasmon resonance energy with a single parameter.