Solvent Control of Surface Plasmon-Mediated Chemical Deposition of Au Nanoparticles from Alkylgold Phosphine Complexes

(Figure presented) Bottom-up approaches to nanofabrication are of great interest because they can enable structural control while minimizing material waste and fabrication time. One new bottom-up nanofabrication method involves excitation of the surface plasmon resonance (SPR) of a Ag surface to drive deposition of sub-15 nm Au nanoparticles from MeAuPPh₃. In this work we used density functional theory to investigate the role of the PPh₃ ligands of the Au precursor and the effect of adsorbed solvent on the deposition process, and to elucidate the mechanism of Au nanoparticle deposition. In the absence of solvent, the calculated barrier to MeAuPPh₃ dissociation on the bare surface is <20 kcal/mol, making it facile at room temperature. Once adsorbed on the surface, neighboring MeAu fragments undergo ethane elimination to produce Au adatoms that cluster into Au nanoparticles. However, if the sample is immersed in benzene, we predict that the monolayer of adsorbed solvent blocks the adsorption of MeAuPPh₃ onto the Ag surface because the PPh₃ ligand is large compared to the size of the exposed surface between adsorbed benzenes. Instead, the Au-P bond of MeAuPPh₃ dissociates in solution (E_a = 38.5 kcal/mol) in the plasmon heated near-surface region followed by the adsorption of the MeAu fragment on Ag in the interstitial space of the benzene monolayer. The adsorbed benzene forces the Au precursor to react through the higher energy path of dissociation in solution rather than dissociatively adsorbing onto the bare surface. This requires a higher temperature if the reaction is to proceed at a reasonable rate and enables the control of deposition by the light induced SPR heating of the surface and nearby solution.