Layer-by-layer assembly of three-dimensional colloidal supercrystals with tunable plasmonic properties.

We present a simple and efficient method for synthesizing large-area (>1 cm(2)), three-dimensional (3D) gold and silver nanoparticle supercrystal films. In this approach, Janus nanoparticle (top face solvent-phobic and bottom face solvent-philic) films with an arbitrary number of close-packed nanoparticle monolayers can be formed using layer-by-layer (LbL) assembly from suspensions of thiolate-passivated gold or silver colloids. Furthermore, we demonstrate that these films can act as true 3D plasmonic crystals with strong transverse (intralayer) and longitudinal (interlayer) near-field coupling. In contrast to conventional polyelectrolyte-mediated LbL assembly processes, this approach allows multiple longitudinal coupling modes with a conspicuous spectral dependence on the layer number. We have found a universal scaling relation between the spectral position of the reflectance dips related to the longitudinal modes and the layer number. This relation can be understood in terms of the presence of a plasmonic Fabry-Perot nanocavity along the longitudinal direction that allows the formation of standing plasmon waves under plasmon resonance conditions. The realization of 3D plasmonic coupling enables broadband tuning of the collective plasmon response over a wide spectral range (visible and near-IR) and provides a pathway to designer plasmonic metamaterials.