A Dibenzo[g,p]chrysene‐Based Organic Semiconductor with Small Exciton Binding Energy via Molecular Aggregation

Abstract Exciton binding energy ( E b ) is understood as the energy required to dissociate an exciton in free‐charge carriers, and is known to be an important parameter in determining the performance of organic opto‐electronic devices. However, the development of a molecular design to achieve a small level of E b in the solid state continues to lag behind. Here, to investigate the relationship between aggregation and E b , star‐shaped π‐conjugated compounds DBC‐RD and TPE‐RD were developed using dibenzo[ g , p ]chrysene (DBC) and tetraphenylethylene (TPE). Theoretical calculations and physical measurements in solution showed no apparent differences between DBC‐RD and TPE‐RD, indicating that these molecules possess similar properties on a single‐molecule level. By contrast, pristine films incorporating these molecules showed significantly different levels of electron affinity, ionization potential, and optical gap. Also, DBC‐RD had a smaller E b value of 0.24 eV compared with that of TPE‐RD (0.42 eV). However, these molecules showed similar E b values under dispersed conditions, which suggested that the decreased E b of DBC‐RD in pristine film is induced by molecular aggregation. By comparison with TPE‐RD, DBC‐RD showed superior performances in single‐component organic solar cells and organic photocatalysts. These results indicate that a molecular design suitable for aggregation is important to decrease the E b in films.