Improving the Performance of Formamidinium and Cesium Lead Triiodide Perovskite Solar Cells using Lead Thiocyanate Additives

Abstract Formamidinium lead triiodide (FAPbI3) is considered as an alternative to methylammonium lead triiodide (MAPbI3) because of its lower band gap and better thermal stability. However, owing to the large size of FA cations, it is difficult to synthesize high‐quality FAPbI3 thin films without the formation of an undesirable yellow phase. Smaller sized cations, such as MA and Cs, have been successfully used to suppress the formation of the yellow phase. Whereas FA and MA lead triiodide perovskite solar cells (PVSCs) have achieved power conversion efficiencies (PCEs) higher than 20 %, the PCEs of formamidinium and cesium lead triiodide (FA1−xCsxPbI3) PVSCs have been only approximately 16.5 %. Herein, we report our examination of the main factors limiting the PCEs of (FA1−xCsxPbI3) PVSCs. We find that one of the main limiting factors could be the small grain sizes (≈120 nm), which leads to relatively short carrier lifetimes. We further find that adding a small amount of lead thiocyanate [Pb(SCN)2] to the precursors can enlarge the grain size of (FA1−xCsxPbI3) perovskite thin films and significantly increase carrier lifetimes. As a result, we are able to fabricate (FA1−xCsxPbI3) PVSCs with significantly improved open‐circuit voltages and fill factors and, therefore, enhanced PCEs. With an optimal 0.5 mol % Pb(SCN)2 additive, the average PCE is increased from 16.18±0.50 (13.45±0.78) % to 18.16±0.54 (16.86±0.63) % for planar FA0.8Cs0.2PbI3 PVSCs if measured under reverse (forward) voltage scans. The champion cell registers a PCE of 19.57 (18.12) % if measured under a reverse (forward) voltage scan, which is comparable to that of the best‐performing MA‐containing planar FA‐based lead halide PVSCs.