This report describes the structural and optical properties of a series of spherical shell/core nanoparticles in which the shell is comprised of a thin layer of gold, silver, or gold-silver alloy, and the core is comprised of a monodispersed silica nanoparticle. The silica core particles were prepared using the Stöber method, functionalized with terminal amine groups, and then seeded with small gold nanoparticles (approximately 2 nm in diameter). The gold-seeded silica particles were coated with a layer of gold, silver, or gold-silver alloy via solution-phase reduction of an appropriate metal ion or mixture of metal ions. The size, morphology, and elemental composition of the composite nanoparticles were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The optical properties of the nanoparticles were analyzed by UV-vis spectroscopy, which showed strong absorptions ranging from 400 nm into the near-IR region, where the position of the plasmon band reflected not only the thickness of the metal shell, but also the nature of the metal comprising the shell. Importantly, the results demonstrate a new strategy for tuning the position of the plasmon resonance without having to vary the core diameter or the shell thickness.

Hollow gold-silver nanoshells having systematically varying sizes between 40 and 100 nm were prepared. These particles consist of a hollow spherical silver shell surrounded by a thin gold layer. By varying the volume of the gold stock solution added to suspensions of small silver-core templates, we tailored the hollow gold-silver nanoshells to possess strong tunable optical extinctions that range from the visible to the near-IR spectral regions, with extinctions routinely centered at ∼950 nm. The size and morphology of these core/shell nanoparticles were characterized by dynamic light scattering (DLS), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). Separately, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were used for measuring their elemental composition; UV-vis spectroscopy was used to evaluate their optical properties. Given their relatively small size compared to other nanoparticles that absorb strongly at near IR wavelengths, these easy-to-synthesize particles should find use in applications that require ultrasmall nanoparticles with extinctions comfortably beyond visible wavelengths (e.g., medicinal therapies, diagnostic imaging, nanofluidics, and display technologies).

The synthesis of gold, palladium, and gold-palladium alloy nanoshells (approximately 15-20 nm thickness) was accomplished by the reduction of gold and palladium ions onto dielectric silica core particles (approximately 100 nm in diameter) seeded with small gold nanoparticles (approximately 2-3 nm in diameter). The size, morphology, elemental composition, and optical properties of the nanoshells were characterized using field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and ultraviolet-visible spectroscopy. The results demonstrate the successful growth of gold, palladium, and gold-palladium alloy nanoshells, where the optical properties systematically vary with the relative content of gold and palladium. The alloy nanoshells are being prepared for use in applications that stand to benefit from photoenhanced catalysis.

We have successfully utilized the newly developed near-infrared multispectral imaging (NIR-MSI) microscope to observe and measure directly the localized surface plasmon absorption (LSPR) of individual gold nanoshells. The NIR-MSI is suited for this task because it can simultaneously record spectral and spatial information of a sample with high sensitivity (single pixel resolution) and high spatial resolution (approximately 0.9 microm/pixel). Importantly, the LSPR of individual nanoshells measured by the NIR-MSI microscope agrees well with the spectra calculated theoretically using Mie scattering for the nanoshells (i.e., nanoshells with silica cores approximately 800 nm in diameter and gold shell thicknesses of approximately 35 nm). Additionally, the NIR-MSI microscope enables measurement of LSPR at different positions within a single nanoshell. LSPR spectra were found to be distinct at various positions within a single nanoshell. Since LSPR spectra are known to depend on the shape and morphology of the nanoshells, these results seem to suggest that the individual nanoshells are not smooth and well-defined, but are rather rough and inhomogeneous. The LSPR spectra of single nanoshells in several different solvents were also examined using NIR-MSI and were found to depend on the dielectric constant of the medium. However, the relationship was discovered to be more complex than simply following the Drude equation. Specifically, when (lambda(max)/fwhm)(2) values of LSPR for single gold nanoshells were plotted as a function of 2n(2) (or 2epsilon) for nanoshells in six different solvents, a linear relationship was found for only three solvents: D(2)O, acetonitrile-d(3), and ethyl acetate. Acetone-d(6) showed a slight deviation, whereas formamide and pyridine-d(5) exhibited distinctly different correlations.