Controlled plasmon resonance properties of hollow gold nanosphere aggregates

Hollow gold nanospheres (HGNs) ranging from 29.9 nm/8.5 nm (outer diameter/shell thickness) to 51.5 nm/4.5 nm and having aspect ratios spanning 3.5-11.7 were employed to investigate the ability to tailor charge oscillations of HGN aggregates by systematic variation of particle aspect ratio, interparticle gap, and nanosphere inner surface spatial separation. Altering these properties in aggregated HGNs led to control over the interparticle plasmon resonance. Thiol-mediated aggregation was accomplished using either ethanedithiol or cysteine, resulting in dimeric structures in which monomer subunits were spatially separated by <3 Å and 1.2 ± 0.7 nm, respectively. Particle dimensions and separation distances were confirmed by transmission electron microscopy. Experimental absorption spectra obtained for high-aspect ratio nanospheres dimerized using ethanedithiol exhibited an obvious blue shift of the surface plasmon resonance (SPR) relative to that observed for the native, monomeric HGN. This spectral difference likely results from a charge-transfer plasmon resonance at the dimer interface. The extent of the blue shift was dependent upon shell thickness. Dimers comprised of thin-shelled HGNs exhibited the largest shift; aggregates containing HGNs with thick shells (≥7 nm) did not display a significant SPR shift when the individual particles were in contact. By comparison, all cysteine-induced aggregates examined in this study displayed large interparticle gaps (>1 nm) and a red-shifted SPR, regardless of particle dimensions. This effect can be described fully by a surface mode coupling model. All experimental measurements were verified by finite difference time domain calculations. In addition, simulated electric field maps highlighted the importance of the inner HGN surface in the interparticle coupling mechanism. These findings, which describe structure-dependent SPR properties, may be significant for applications derived from the plasmonic nanostructure platform.