Direct Observation of Increased Free Carrier Generation Owing to Reduced Exciton Binding Energies in Polymerized Small-Molecule Acceptors.

Energy loss caused by exciton binding energy ( E b ) has become a key factor that restricts further advancement of organic solar cells (OSCs). Herein, we used transient mid-IR spectroscopy to study direct photogeneration of free charge carriers in small-molecule acceptors (SMAs) Y6 and IDIC as well as polymerized SMAs (PSMAs) PYFT and PZ1. We found that free carrier concentration is higher in PSMAs than in their corresponding SMAs, indicating reduced exciton E b , which is then confirmed by ultraviolet photoelectron spectroscopy, low-energy inverse photoemission spectroscopy, and film absorption spectra measurements. The measured E b values of PYFT and PZ1 are 0.24 and 0.37 eV, respectively, smaller than those of Y6 (0.32 eV) and IDIC (0.47 eV). This work not only provides a method to directly monitor the photogenerated free carriers in OSC materials but also demonstrates that polymerization is an effective strategy to reduce the E b , which is crucial to decrease the energy losses in high-performance OSCs.