Novel Phenothiazine‐Based Self‐Assembled Monolayer as a Hole Selective Contact for Highly Efficient and Stable p‐i‐n Perovskite Solar Cells

Abstract Recent advances in perovskite solar cells (PSCs) performance have been closely related to improved interfacial engineering and charge selective contacts. Here, a novel and cost‐competitive phenothiazine based, self‐assembled monolayer (SAM) as a hole‐selective contact for p‐i‐n PSCs is introduced. The molecularly tailored SAM enables an energetically well‐aligned interface with the perovskite absorber, with minimized nonradiative interfacial recombination loss, thus dramatically improving charge extraction/transport and device performance. The resulting PSCs exhibit a power conversion efficiency (PCE) of up to 22.44% (certified 21.81%) with an average fill factor close to 81%, which is among the highest efficiencies reported to date for p‐i‐n PSCs. The new SAM also demonstrates the outstanding operational stability of the PSC, with increasing PCE from 20.3% to 21.8% during continuous maximum power point tracking under a simulated 1 sun illumination for 100 h. The reported findings highlight the great potential of engineered SAMs for the fabrication of stable and high performing PSCs.