Effect of Heterocyclic Anchoring Sequence on the Properties of Dithienogermole-Based Solar Cells

The synthesis and characterization of two new small molecular donor materials, DTGe­(ThFBTTh2)2 and DTGe­(FBTTh3)2, are presented for application in organic solar cells. These two materials represent structural evolutions of the high-efficiency, dithienogermole (DTGe)-cored small molecule DTGe­(FBTTh2)2, in which the conjugation length in the backbone was extended by incorporating additional thiophene units. Using the same molecular framework, we have evaluated how the anchoring sequence of heterocyclic units influences material properties and function in solar cell devices. It was found that incorporating additional thiophene units into the backbone, regardless of the position in the molecular platform, caused a small reduction in band gaps; however, both highest occupied molecular orbitals and lowest unoccupied molecular orbital energy bands were at lower energies when the thiophenes were incorporated near the terminus of the molecule. The film morphologies of both materials could be controlled by either thermal or solvent vapor annealing to yield phase separation on the order of tens of nanometers and improved crystallinity. Peak power–conversion efficiencies of 3.6% and 3.1% were obtained using DTGe­(ThFBTTh2)2 and DTGe­(FBTTh3)2, after solvent vapor treatment and thermal annealing, respectively. Our study provides a detailed analysis of how the ordering sequence of heterocyclic building blocks influences the properties and function of organic solar cells.