In Situ Monitoring of Scale Effects on Phase Selection and Plasmonic Shifts during the Growth of AgCu Alloy Nanostructures for Anticounterfeiting Applications

Tailoring of plasmon resonances is essential for applications in anticounterfeiting. This is readily achieved by tuning the composition of alloyed metal clusters; in the simplest case, binary alloys are used. Yet, one challenge is the correlation of cluster morphology and composition with the changing optoelectronic properties. Hitherto, the early stages of metal alloy nanocluster formation in immiscible binary systems such as silver and copper have been accessible by molecular dynamics (MD) simulations and transmission electron microscopy (TEM). Here, we investigate in real time the formation of supported silver, copper, and silver-copper-alloy nanoclusters during sputter deposition on poly(methyl methacrylate) by combining in situ surface-sensitive X-ray scattering with optical spectroscopy. While following the transient growth morphologies, we quantify the early stages of phase separation at the nanoscale, follow the shifts of surface plasmon resonances, and quantify the growth kinetics of the nanogranular layers at different thresholds. We are able to extract the influence of scaling effects on the nucleation and phase selection. The internal structure of the alloy cluster shows a copper-rich core/silver-rich shell structure because the copper core yields a lower mobility and higher crystallization tendency than the silver fraction. We compare our results to MD simulation and TEM data. This demonstrates a route to tailor accurately the plasmon resonances of nanosized, polymer-supported clusters which is a crucial prerequisite for anticounterfeiting.