Unravelling the Self-Assembly of Diketopyrrolopyrrole-Based Photovoltaic Molecules

The nanostructure of bulk heterojunction in an organic solar cell dominating the electron transport process plays an important role in improving the device efficiency. However, there is still a great need for further understanding the local nanostructures from the viewpoint of molecular design because of the complex alignment in the solid film. In this work, four kinds of photovoltaic materials containing a diketopyrrolopyrrole (DPP) unit combined with other different building blocks were selected and their self-assembled structures on a solid surface were studied by scanning tunneling microscopy technique in combination with theory calculations. The results reveal these DPP-based photovoltaic molecules self-assembled into different nanostructures, which strongly depend on the chemical structure, in particular the backbones and alkyl side chains. The planarities of backbones are affected both by molecule-substrate interaction and steric hindrance induced by the substituted thiophene or benzo[ b]thiophene units on DPP and porphyrin building blocks. The substituted branched alkyl side chains are out of the plane, which are influenced by the alignments of molecular backbones. In addition, the solution concentration also shows a large effect on the self-assembled nanostructures. This systematic research on the self-assembled structures of DPP-based semiconductors on a surface would provide guidance for designing materials and controlling the morphology of a donor/acceptor heterojunction system.