Langmuir and Langmuir–Blodgett Films of Gold and Silver Nanoparticles

Recently the focus of the Langmuir–Blodgett technique as a method of choice to transfer monolayers from the air/water interface onto solid substrates in a controllable fashion has been shifting toward purely hydrophobic gold and silver nanoparticles. The fundamental interactions between particles that become relevant in the absence of polar groups range from dispersive attractions from the metal cores and repulsions between ligand shells to weaker entropic factors. The layer evolution is explored, starting with interfacial self-assembly upon solution spreading and domain and circular island formation, which subsequently merge into a complete monolayer and finally form multilayers or macroscopic wrinkles. Moreover, structural properties such as the core:ligand size ratio are investigated in the context of dispersive forces, whereby the nanoparticles with small cores and long ligands tend not to aggregate sufficiently to produce continuous films, those with large cores and short ligands were found to aggregate irreversibly, and those in between the two extremes were concluded to be able to form highly organized crystalline films. Similarly, the characteristics of the spreading solution such as the concentration and the solvent type crucially influence the film crystallinity, with the deciding factor being the degree of affinity between the capping ligand and the solvent used for spreading. Finally, the most common strategies employed to enhance the mechanical stability of the metal nanoparticle films along with the recent attempts to functionalize the particles in attempts to improve their applicability in the industry are summarized and evaluated in relation to their future prospects. One of the objectives of this feature article is to elucidate the differences between hydrophobic metal nanoparticles and typical amphiphilic molecules that the majority of the literature in the field describes and to familiarize the reader with the knowledge required to design Langmuir–Blodgett nanoparticle systems as well as the strategies to improve existing ones.