Localized surface plasmon of quasi-one-dimensional metallic nanostructures.

摘要

The plasmon resonance of noble metal nanoparticles provides interesting optical properties in the visible and near-infrared region, and is highly tunable by varying the shape and the composition of the nanoparticles. The rod-like gold nanostructures can be synthesized by a seed-mediated method in aqueous surfactant solutions. Starting from different types of gold seeds, either single crystalline gold nanorods or penta-fold twinned gold bipyramids can be synthesized in decent yield with silver(I) added into the growth solution. These nanostructures have pronounced plasmon resonance varying in the 1∼2 eV range. The bipyramids are strikingly monodisperse in shape, which leads to the sharpest ensemble longitudinal plasmon resonance reported so far for metal colloid solutions. A mechanism based on the underpotential deposition of silver was thus suggested to explain the essential role of Ag(I) in the growth process.;The optical spectra of the gold colloids were simulated with the finite-difference time-domain (FDTD) method. The results show excellent agreement with recent experimental optical spectra. The local field enhancement (|E|/|E0|) was studied at the plasmon resonance. Sharper structural features produce more significant enhancement and the largest enhancement of more than a factor of 200 is seen around the poles of the bipyramid. A large internal field enhancement by more than a factor of 30 is found for the bipyramids, which suggests that they will exhibit very strong optical nonlinearities.;The plasmon can be further tuned by introducing the core/shell nanostructures such as metal/metal or metal/semiconductor nanorods. Following a simple procedure, a homogeneous layer of silver with 1-4 nm thickness can be plated onto the gold nanorods, which shifts the longitudinal plasmon mode of the nanorods toward blue. The silver layer can be converted to semiconductors silver sulfide or selenide, with the longitudinal plasmon resonance tuned toward red. The metal/semiconductor nanorods also present significant nonlinear optical properties.;Finally, the optical properties of plasmon at low temperature were studied. Combining the experimental and theoretical work on this topic, it is found that the electron-phonon relaxation becomes less active, implying a higher quality factor of the plasmon resonance and therefore larger local field enhancement at lower temperature.