Matrix effects on the surface plasmon resonance of dry supported gold nanocrystals

We present a method to characterize surface-chemical properties of gold nanocrystals. Spherical, 60 nm gold nanocrystals were immobilized on quartz substrates by a coupling agent and cleaned in a hydrogen plasma. The nanocrystals were then functionalized with alkanethiol self-assembled monolayers (SAM) of varying chain lengths by adsorption from the gas phase, and localized surface plasmon resonance (LSPR) spectroscopy was performed on the samples. Depending on the alkanethiol chain length, the adsorption of the SAM redshifted the LSPR to different extents, in accordance with Mie theory. SAM thickness differences below 1 nm could be easily resolved. Our results demonstrate that LSPR spectroscopy can be applied to characterize thin organic layers on dry supported gold particles with high sensitivity.