The impact of surface chemistry on the interfacial evaporation-driven self-assembly of thermoplasmonic gold nanoparticles

This paper reports an interfacial evaporation-driven approach for self-assembly of a gold nanoparticle (AuNP) film at the interface of liquid/air. We have designed colloidal plasmonic AuNPs capped with different types and surface coverage densities of ligands (i.e. purified and unpurified oleylamine-capped or thiol-protected AuNPs) and studied the impact of surface chemistry on the self-assembly of AuNPs using the optically excited plasmonic heating effect. By employing the extended DerjaguinLandau-Verwey-Overbeek model, the calculated lowest potential energies of the assembled AuNPs capped with purified oleylamine or alkyl thiols are between -1 k_BT and -2 k_BT, which is close to the room temperature thermal energy and represents a meta-stable assembly, indicating the reversible self-assembly of the AuNP film observed from the experiment. Furthermore, we observed the superheating phenomenon in well-dispersed nanoparticle solution while normal boiling occurred in the solutions with AuNP assemblies. The SERS activity of the as-prepared AuNP film has also been studied using rhodamine 6G as a molecular probe. This work not only provides a new aspect of the boiling phenomena of optically heated colloidal plasmonic nanoparticle solutions, but also provides inspiration for a new approach in designing surface ligands on the nanoparticles to realize reversible self-assembly via interfacial evaporation.