Dithieno[3,2-b:2',3'-d]pyrrole Cored p-Type Semiconductors Enabling 20 % Efficiency Dopant-Free Perovskite Solar Cells.

Organic p-type semiconductors with tunable structures offer great opportunities for hybrid perovskite solar cells (PVSCs). We report herein two dithieno[3,2-b:2',3'-d]pyrrole (DTP) cored molecular semiconductors prepared through π-conjugation extension and an N-alkylation strategy. The as-prepared conjugated molecules exhibit a highest occupied molecular orbital (HOMO) level of -4.82 eV and a hole mobility up to 2.16×10-4  cm2 V-1 s-1 . Together with excellent film-forming and over 99 % photoluminescence quenching efficiency on perovskite, the DTP based semiconductors work efficiently as hole-transporting materials (HTMs) for n-i-p structured PVSCs. Their dopant-free MA0.7 FA0.3 PbI2.85 Br0.15 devices exhibit a power conversion efficiency over 20 %, representing one of the highest values for un-doped molecular HTMs based PVSCs. This work demonstrates the great potential of using a DTP core in designing efficient semiconductors for dopant-free PVSCs.

Correlating Hysteresis and Stability with Organic Cation Composition in the Two-Step Solution-Processed Perovskite Solar Cells.

The two-step solution-based process has demonstrated substantial success in fabricating high-efficiency perovskite solar cells in recent years. Despite the high performance, the underlying mechanisms that govern the formation of perovskite films and corresponding device performance are yet to be fully understood. Particularly, organic cation composition used in the two-step solution processing of mixed-cation lead halide perovskite solar cells plays a critical role in the perovskite film formation and the resultant device performance. However, little is understood about the impacts of organic cation composition on the current density-voltage (J-V) hysteretic behavior and stability of perovskite solar cells. To address this need, here, we study the effect of mixed organic cations, that is, the fraction of formamidinium (FA) and methylammonium (MA) contents, used for the two-step solution-processed perovskite thin films on solar cell performance, including efficiency, J-V hysteresis, and stability. In addition to the efficiency variations, we find that perovskite solar cells based on FA-rich and MA-rich stoichiometries show distinct characteristics in J-V hysteresis and stability. The origins of such a discrepancy are attributed to the thermodynamically driven conversion from lead iodide to perovskites, which is determined by the combination of organic cations. The perovskite solar cells based on the mixed cation FA0.6MA0.4PbI3 composition show a champion power conversion efficiency of over 21% and robust stability (retaining more than 90% of initial efficiency) under maximum power-point tracking in dry nitrogen for more than 500 h. Our work provides insights on understanding the formation of perovskite films in the two-step process, which may benefit further investigation on perovskite solar cells.