Donor-π-donor type hole transporting materials: marked π-bridge effects on optoelectronic properties, solid-state structure, and perovskite solar cell efficiency.

Donor-π-bridge-donor type oligomers (D-π-D) have been studied intensively as active materials for organic optoelectronic devices. In this study, we introduce three new D-π-D type organic semiconductors incorporating thiophene or thienothiophene with two electron-rich TPA units, which can be easily synthesized from commercially available materials. A thorough comparison of their optoelectronic and structural properties was conducted, revealing the strong influence of the extent of longitudinal π-bridge conjugation on both the solid structure of the organic semiconductive materials and their photovoltaic performance when applied as hole transporting materials (HTM) in perovskite solar cells. Single-crystal measurements and time-resolved photoluminescence (TRPL) studies indicate that these coplanar donor-π-donor type HTMs could be promising alternatives to state-of-the-art spiro-OMeTAD, due to the multiple intermolecular short contacts as charge transporting channels and efficient charge extraction properties from the perovskite layer. The optimized devices with PEH-9 exhibited an impressive PCE of 16.9% under standard global AM 1.5 illumination with minimized hysteretic behaviour, which is comparable to that of devices using spiro-OMeTAD under similar conditions. Ambient stability after 400 h revealed that 93% of the energy conversion efficiency was retained for PEH-9, indicating that the devices had good long-term stability.