Low‐Dimensional 2‐thiopheneethylammonium Lead Halide Capping Layer Enables Efficient Single‐Junction Methylamine‐Free Wide‐Bandgap and Tandem Perovskite Solar Cells

Abstract Wide‐bandgap (WBG) perovskite solar cells (PSCs) have garnered significant attention for their potential applications in tandem solar cells. However, their large open‐circuit voltage (V_OC) deficit and serious photo‐induced halide segregation remain the main challenges that impede their applications. Herein, a post‐treatment strategy without thermal annealing is presented to form a 2D top layer of 2‐thiopheneethylammonium lead halide (n = 1) on WBG perovskites. This thermal annealing‐free post‐treatment method can more effectively passivate the defects of WBG methylamine (MA)‐free formamidinium/cesium lead iodide/bromide perovskite films and suppress photo‐induced perovskite phase segregation, as compared with the thermal annealing method that yields multi‐2D phases. The resulting opaque and semi‐transparent 1.66 eV‐bandgap perovskite solar cells deliver maximum power conversion efficiencies of 21.47% (a small V_OC deficit of 0.43 V) and 19.11%, respectively, both of which are among the highest reports for inverted MA‐free WBG PSCs. Consequently, four‐terminal all‐perovskite tandem cells realize a remarkable efficiency of 26.64%, showing great promise for their applications in efficient multi‐junction tandem solar cells.