Charge Transfer at Hybrid Interfaces: Plasmonics of Aromatic Thiol-Capped Gold Nanoparticles

Although gold nanoparticles stabilized by organic thiols are the building blocks in a wide range of applications, the role of the ligands on the plasmon resonance of the metal core has been mostly ignored until now. Herein, a methodology based on the combination of spectroscopic ellipsometry and UV-vis spectroscopy is applied to extract dielectric functions of the different components. It is shown that aromatic thiols allow a significant charge transfer at the hybrid interface with the s and d bands of the gold core that yields "giant" red shifts of the plasmon band, up to 40 nm for spherical particles in the size range of 3-5 nm. These results suggest that hybrid nanoplasmonic devices may be designed through the suitable choice of metal core and organic components for optimized charge exchange.