Halogen-bonding mediated stepwise assembly of gold nanoparticles onto planar surfaces

In this study halogen bonding (XB) is used as the driving force for the noncovalent assembly of gold nanoparticles (AuNPs) on silicon and quartz substrates functionalized with organic monolayers. The AuNPs are functionalized with XB-donor ligands, whereas the monolayers have pyridine groups as XB-acceptors. The surface-confined systems are formed by iteratively exposing the monolayers to solutions of organic cross-linkers having 2-4 pyridine groups and functionalized AuNPs. UV-vis spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM) reveal how the structure of the resulting surface-bound assemblies are controlled by (i) the properties of the monolayers, (ii) the molecular structure and the number of XB binding sites of the organic cross-linker, and (iii) the number of functionalized AuNP and cross-linker deposition steps. Moreover, these structures exhibit surface-enhanced Raman scattering and significant changes are observed in the morphology of some of the surface-bound assemblies upon aging.