LAUSR

Deposition of the top‐contact electrode to create large‐area electrode | monolayer | electrode junctions represents a contemporary challenge to the integration of molecular electronic phenomena into device structures. Here, a top contact electrode is formed on top of an organic monolayer over a large area (cm2) by two simple, sequential self‐assembly steps. Initial self‐assembly of 4,4′‐(1,4‐phenylenebis(ethyne‐2,1‐diyl))dianiline onto gold‐on‐glass substrates gives high‐quality monolayers. The exposed amine functionality is subsequently used to anchor uncapped gold nanoparticles deposited in a second self‐assembly step. These uncapped gold nanoparticles are prepared by thermolysis of lipoic acid stabilized gold nanoclusters and contain gold oxide (≈9%) that provides stability in the absence of an organic capping ligand. This two‐step procedure results in full coverage of the monolayer by the densely packed gold nanoparticles, which spontaneously condense to give a semi‐continuous film. The electrical properties of these junctions are determined from I–V curves, revealing uniform electrical response and absence of metallic short‐circuits or evidence of damage to the underlying molecular monolayer. These promising electrical characteristics suggest that the deposition of uncapped gold nanoparticles on suitably functionalized molecular monolayers provides a path for the fabrication of molecular electronic devices using simple methodologies.