The self-assembly of monodisperse inorganic nanoparticles into highly ordered arrays (superlattices) represents an exciting route to materials and devices with new functions. It allows programming their properties by varying the size, shape, and composition of the nanoparticles, as well as the packing order of the assemblies. While substantial progress has been achieved in the fabrication of superlattice materials made of nanospheres, limited advances have been made in growing similar materials with anisotropic building blocks, which is particularly true for free-standing two-dimensional superlattices. In this paper, we report the controlled growth of free-standing, large-area, monolayered gold-nanorod superlattice sheets by polymer ligands in an entropy-driven interfacial self-assembly process. Furthermore, we experimentally characterize the plasmonic properties of horizontally aligned sheets (H-sheets) and vertically aligned sheets (V-sheets) and show that observed features can be well described using a theoretical model based on the discrete-dipole approximation. Our polymer-ligand-based strategy may be extended to other anisotropic plasmonic building blocks, offering a robust and inexpensive avenue to plasmonic nanosheets for various applications in nanophotonic devices and sensors.
© 2011 American Chemical Society