Increased Sensitivity of Surface Plasmon Resonance of Gold Nanoshells Compared to That of Gold Solid Colloids in Response to Environmental Changes

Gold nanoshells have been synthesized by reacting aqueous HAuCl4 solutions with solid templates such as silver nanoparticles. The morphology, void space, and wall thickness of these hollow nanostructures were all determined by the templates, which were completely converted into soluble species during the replacement reaction. The surface plasmon peaks of these gold nanoshells were considerably red-shifted as compared to gold solid colloids having approximately the same dimensions. In addition, the surface plasmon resonance of gold nanoshells exhibited a much more sensitive response toward environmental changes even when compared with solid colloids with a mean size much smaller than that of gold nanoshells. For example, the sensitivity factor (i.e., the shift in peak position per unit change in the refractive index of the surrounding medium) was 408.8, 60.0, and 70.9 nm per refractive index unit for gold nanoshells with a mean diameter of 50 nm and wall thickness of 4.5 nm, gold solid colloids of 50 nm in diameter, and gold solid colloids of 30 nm in diameter, respectively. The formation of alkanethiolate self-assembled monolayers on their surfaces caused the plasmon peaks to red-shift by 3.0 nm per methylene unit for gold nanoshells and 0.2 nm per methylene unit for solid colloids with a mean size of 50 nm. Such enhanced sensitivities should make gold nanoshells particularly useful as optical probes for chemical or biological binding events at solid-liquid interfaces.