Selective embedment of silver nanocrystals into spatially segregated domains in thin polymer films for controlled fabrication of functional nanocomposites

Fabrication of polymer-nanoparticle nanocomposites typically relies on mixing nanoparticle and polymer solutions, which renders little control over nanoparticle incorporation, and homogeneity of the resulting composite material. This work focuses on the thermally induced embedment of monocrystalline silver nanocubes (AgNCs) into polymer surfaces. The AgNCs are initially deposited through a Langmuir approach onto films of immiscible blended polymer films, which allows fine control over nanoparticle density and aggregation state. This nanoparticle/polymer composite is then heated above the glass transition temperature (T(g)) of a polymer, which initiates the irreversible embedding of the AgNCs. The immiscible ternary polymer films featured discrete domains (with different T(g)s), which were altered by changing the amount of polystyrene, poly(2-vinylpyridine) and poly(methyl methacrylate) within the polymer solution. The T(g) dependence of the embedding process allowed the selective embedment of AgNCs into discrete polymer domains. The process was monitored in real time by using spatially separated hybrid plasmon modes, through peak shifts observed in a UV-vis spectrum. Enhanced surface confinement was observed for certain tripolymer films when compared to polystyrene–AgNC nanocomposites, due to changes in the surface energy within the blend. This work brings interesting insight on nanoparticle-blended polymer interactions and provides a fairly universal approach for the fabrication of these polymer–metal nanoparticle nanocomposites, which is of particular interest in fields that require fine control over nanoparticle incorporation within segregated polymer domains.