While top-down lithographic techniques are the most technologically developed routes for the fabrication of nanostructured interfaces, there lie several challenges and intrinsic deficiencies in those methods. For instance, geometries that can be fabricated by atomic or molecular deposition followed by etching processes are typically limited to primitive planar geometries of a single element. . Thus, the applications that require tunability of optical properties by, for instance, complex geometries, facetdependent chemistry, hybrid metal/metal and metal/metal oxide coupling, are not easily feasible with those techniques. In some fields, such as plasmonics, the polycrystalline nature of nanostructures fabricated by lithographic techniques can even have detrimental effects. Moreover, the fabrication of sub-30 nm structures with lithographic techniques is still a challenge. The self-assembly technique, on the other hand, is intrinsically free from these drawbacks. With the rapid advancement in the field of wet-chemical synthesis processes, nanostructures of complex geometry and composition with sizes going down to <5 nm can be synthesized with relative ease and low cost. Self-assembly of such nanostructures as building blocks to form functional interfaces provides greater flexibility to obtain complex structures inaccessible by lithographic techniques.