Tunable orientation of two-dimensional assembled Au octahedron superlattices in polymer films as flexible SERS substrates

Anisotropic nanoparticles have been widely used as building blocks for preparing surface-enhanced Raman spectroscopy (SERS) substrates. However, tailoring the SERS activity at the self-assembly level through the anisotropic nanoparticle orientation is a big challenge, mainly due to the lack of simple assembly methods. In the present work, we report an air-water interface mediated co-assembly (AWIMCoA) strategy to prepare flexible 2D superlattices of Au octahedra with tunable orientations. We have demonstrated that Au octahedra can self-assemble into face-up, edge-up and vertex-up orientations on changing the surface wettability of Au octahedra, which determines the interparticle anisotropic interactions and the interaction between Au octahedra and the poly(styrene-ethylene-butylene-styrene) (SEBS) nanomembrane. The effect of assembly orientation on the SERS performance of 2D superlattices has been studied through correlated SEM characterization and SERS mapping. Among all the orientational modes, flexible 2D superlattices with the vertex-up orientation show the highest enhancement performance and uniformity, which is further demonstrated by theoretical simulation. Partially embedded 2D superlattices in the SEBS nanomembrane are robust to remove the surface ligands without breaking the whole nanostructure. This post-treatment process boosts the SERS performance of the 2D superlattice with the edge-up orientation by forming fused nanostructures among neighboring Au octahedra. We expect that the co-assembly method will be widely applied in the preparation of reusable and high-performance SERS substrates for broad application.