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The properties of polymeric nanofibers can be tailored and enhanced byproperly managing the structure of the polymeric molecules at the nanoscale.Although electrospun polymer fibers are increasingly exploited in manytechnological applications, their internal nanostructure, determining theirimproved physical properties, is still poorly investigated and understood.Here, we unravel the internal structure of electrospun functional nanofibersmade by prototype conjugated polymers. The unique features of near fieldoptical measurements are exploited to investigate the nanoscale spatialvariation of the polymer density, evidencing the presence of a dense internalcore embedded in a less dense polymeric shell. Interestingly, nanoscale mappingthe fiber Young's modulus demonstrates that the dense core is stiffer than thepolymeric, less dense shell. These findings are rationalized by developing atheoretical modeling and simulations of the polymer molecular structuralevolution during the electrospinning process. This model predicts that thestretching of the polymer network induces a contraction towards the jet centerof the network with a local increase of the polymer density, as observed in thesolid structure. The found complex internal structure opens interestingperspective for improving and tailoring the molecular morphology andmultifunctional electronic and optical properties of polymer fibers.

Local mechanical properties of electrospun fibers correlate to their internal nanostructure