Hierarchical assembly of light-emitting polymer nanofibers in helical morphologies

Single electrospun nanofibers of light-emitting conjugated polymers hierarchically assemble at nano- to macroscopic lengthscales in various helical morphologies. At nanoscopic lengthscales, molecular chains follow the microscopic assembly, prevalently aligning along the fiber dynamic axis, as demonstrated by polarized photoluminescence spectroscopy. The role of molecular weight in the resulting assembling and optical properties is highlighted and discussed. Nanofibers based on the heaviest polymer exhibit the most stretched helical geometries and the highest suppression of the excitonic energy migration, resulting in the most blue-shifted photoluminescence with respect to thin films.