Using adsorption kinetics to assemble vertically aligned nanorods at liquid interfaces for metamaterial applications.

Vertically aligned monolayers of metallic nanorods have a wide range of applications as metamaterials or in surface enhanced Raman spectroscopy. However the fabrication of such structures using current top-down methods or through assembly on solid substrates is either difficult to scale up or have limited possibilities for further modification after assembly. The aim of this paper is to use the adsorption kinetics of cylindrical nanorods at a liquid interface as a novel route for assembling vertically aligned nanorod arrays that overcomes these problems. Specifically, we model the adsorption kinetics of the particle using Langevin dynamics coupled to a finite element model, accurately capturing the deformation of the liquid meniscus and particle friction coefficients during adsorption. We find that the final orientation of the cylindrical nanorod is determined by their initial attack angle when they contact the liquid interface, and that the range of attack angles leading to the end-on state is maximised when nanorods approach the liquid interface from the bulk phase that is more energetically favorable. In the absence of an external field, only a fraction of adsorbing nanorods end up in the end-on state (≲40% even for nanorods approaching from the energetically favourable phase). However, by pre-aligning the metallic nanorods with experimentally achievable electric fields, this fraction can be effectively increased to 100%. Using nanophotonic calculations, we also demonstrate that the resultant vertically aligned structures can be used as epsilon-near-zero and hyperbolic metamaterials. Our kinetic assembly method is applicable to nanorods with a range of diameters, aspect ratios and materials and therefore represents a versatile, low-cost and powerful platform for fabricating vertically aligned nanorods for metamaterial applications.

Photostability enhancement of InP/ZnSe/ZnSeS/ZnS quantum dots by plasmonic nanostructures.

The effect of gold and silver plasmonic films on the photoluminescence and photostability of InP/ZnSe/ZnSeS/ZnS nanocrystals (quantum dots) is reported. Colloidal gold films promote the photostability enhancement of InP/ZnSe/ZnSeS/ZnS quantum dots (more durable emission properties in the presence of metal nanostructures) through reducing exciton lifetime. In contrast, silver decreases the photostability of InP/ZnSe/ZnSeS/ZnS quantum dots without changing the photoluminescence intensity and kinetics. By adjusting the excitation wavelength closer to the extinction band of gold nanoparticles a 1.8-fold enhancement of luminescence intensity has been obtained using a polyelectrolyte spacer between the metal and InP/ZnSe/ZnSeS/ZnS nanoparticles. Thus, plasmonics offers essential practical improvement of light emitters in terms of their durable luminescent properties upon prolonged optical excitation without losses in luminescence efficiency or even along with increased efficiency.