Organic Semiconductor/Gold Interface Interactions: From Physisorption on Planar Surfaces to Chemical Reactions with Metal Nanoparticles

The interaction of gold nanoparticles (AuNPs) with prototypical organic semiconductors used in optoelectronics, namely, tris(8-hydroxyquinoline)aluminium (Alq(3)) and 4,4-bis[N-(1-naphthyl)-N-phenylamino]diphenyl (-NPD), is investigated in situ by X-ray photoelectron spectroscopy (XPS). These AuNPs-on-molecule experiments are compared with the reversed molecule-on-Au cases. The molecules-on-Au systems show only weak interactions, and the evolution of the XP spectra is dominated by final-state effects. In contrast, in the AuNPs-on-molecules cases, both initial-state effects and final-state effects occur. Spectral features arising for both molecules and metal indicate charge transfer and the formation of organometallic complexes (initial-state effects). The energy shift in the metal emission underlines the size-induced nanometric nature of the molecule/Au interaction (final-state effects). Consequently, the chemical interaction between metals and organic semiconductors likely depends strongly on the deposition sequence in general.