Hydrogen Bonding Stabilized Self-Assembly of Inorganic Nanoparticles: Mechanism and Collective Properties

Developing a simple and efficient method to organize nanoscale building blocks into ordered superstructures, understanding the mechanism for self-assembly and revealing the essential collective properties are crucial steps toward the practical use of nanostructures in nanotechnology-based applications. In this study, we showed that the high-yield formation of ZnO nanoparticle chains with micrometer length can be readily achieved by the variation of solvents from methanol to water. Spectroscopic studies confirmed the solvent effect on the surface properties of ZnO nanoparticles, which were found to be critical for the formation of anisotropic assemblies. Quantum mechanical calculations and all atom molecular dynamic simulations indicated the contribution of hydrogen bonding for stabilizing the structure in water. Dissipative particle dynamics further revealed the importance of solvent nanoparticle interactions for promoting one-dimensional self-assembly. The branching of chains was found upon aging, resulting in the size increase of the ensembles and network formation. Steady-state and time-resolved luminescent spectroscopes, which probed the variation of defect-related emission, revealed stronger Forster resonance energy transfer (FRET) between nanoparticles when the chain networks were formed. The high efficiency of FRET quenching can be ascribed to the presence of multiple energy transfer channels, as well as the short internanoparticle distances and the dipole alignment.