Ordered Au Nanoparticle Array on Au(111) through Coverage Control of Precursor Metal−Organic Chains

Abstract

Metal–organic overlayer structures formed by 1,4-phenylene-diisocyanide (PDI) and Au adatoms on Au(111) in UHV, their stability in air, and the tip-induced Au nanoparticle formation on PDI–Au(111) surfaces in air were investigated using scanning tunneling microscopy (STM) and vibrational spectroscopy. This study reveals that the distribution of Au nanoparticles created during tip-induced release of Au atoms from molecule-Au adatom complexes shows strong dependence on the PDI coverage. Ordered Au nanoparticle arrays form in the medium-coverage regime, while more disordered distributions are observed at low and saturation coverages. The different distributions of Au nanoparticles are a direct consequence of the coverage-dependent assembly of (PDI–Au)n chains, their different stability in air, and a templating effect of the Au(111) surface, which is most pronounced for medium coverage, where phases of densely packed (PDI–Au)n chains and disordered PDI–Au assemblies are confined, respectively, to the fcc and hcp regions of the (22 × √3) surface reconstruction of Au(111). The Au nanoparticles nucleate preferentially in the disordered or defective regions of the PDI–Au precursor overlayer, and their formation requires ambient air and high negative tip-bias, suggesting an electrochemical initiation of Au release from the molecule–Au adatom complexes.