All-small-molecule organic solar cells with over 14% efficiency by optimizing hierarchical morphologies.

The high efficiency all-small-molecule organic solar cells (OSCs) normally require optimized morphology in their bulk heterojunction active layers. Herein, a small-molecule donor is designed and synthesized, and single-crystal structural analyses reveal its explicit molecular planarity and compact intermolecular packing. A promising narrow bandgap small-molecule with absorption edge of more than 930 nm along with our home-designed small molecule is selected as electron acceptors. To the best of our knowledge, the binary all-small-molecule OSCs achieve the highest efficiency of 14.34% by optimizing their hierarchical morphologies, in which the donor or acceptor rich domains with size up to ca. 70 nm, and the donor crystals of tens of nanometers, together with the donor-acceptor blending, are proved coexisting in the hierarchical large domain. All-small-molecule photovoltaic system shows its promising for high performance OSCs, and our study is likely to lead to insights in relations between bulk heterojunction structure and photovoltaic performance.