Depletion-Mediated Interfacial Assembly of Semiconductor Nanorods.

Electronic devices comprised of nanocrystal (NC) thin film are projected to demonstrate enhanced figure of merit if NC building blocks self-assemble into highly uniform, 2-dimensional (2-D) superstructures with long-range order. Despite intensive research efforts and remarkable progress, long-range assembly of colloidal anisotropic NCs into thin films with orientational and positional order has remained to be addressed. One of the most promising approaches is to dissolve excess free molecules into NC solution, which has enabled the formation of NC monolayers with exceptional quality at air/solution interface. Nevertheless, the assembly mechanism and the role of free molecules have not been comprehensively elucidated, restricting the use of the approach. Here, we find that the interfacial assembly of CdSe/CdS core/shell nanorods (NRs) results in various ordered structures in the presence of free oleic acid molecules. The structures include a bundle of standing NRs, a belt of multilayered lying NRs, and a monolayer smectic phase, obtained by simple change in density of surface ligands on the NRs. Experimental observation and theoretical calculation reveal that the assembly is initiated at the air/solution interface due to the preferential depletion attraction of NRs to the interface. However, subsequent growth is significantly altered depending on the ligand density that determines the relative magnitude of interface-NR depletion attraction to inter-NR attraction. Highly ordered structures of NRs, especially for the monolayer smectic phase, are promising as a polarized light-emitting layer for thin-film optical devices. In addition, our findings on the depletion-mediated NR assembly provide important and universal design criteria for 2-D structuring of NCs with diverse geometries and compositions.