Abstract 

We demonstrated a facile route to the preparation of self‐assembled poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐TrFE)] nanodots from spin‐coated thin films. We found that the initial film thickness would play an important role in the formation of such P(VDF‐TrFE) nanodots. Interestingly, the electric dipoles of such nanodots were self‐aligned toward the bottom electrode and their ferroelectric properties were determined by using piezoresponse force microscopy. In addition, the self‐polarized ferroelectric nanostructures were introduced to small molecular organic photovoltaic devices and allowed for enhancing the short circuit current density (Jsc) from 9.4 mA/cm2 to 10.2 mA/cm2 and the power conversion efficiency from 2.37% to 2.65%.