Potassium‐Induced Phase Stability Enables Stable and Efficient Wide‐Bandgap Perovskite Solar Cells

Wide‐bandgap perovskites have great potential to enable high‐efficiency tandem photovoltaics by combining with the well‐established low‐bandgap absorbers. However, such wide‐bandgap perovskites are often necessarily constructed with a high Br content, and thus faced with issues of phase segregation–induced photoinstability and high defect density, severely hindering their photovoltaic performance. Herein, a remarkable boost of the stability and efficiency of wide‐bandgap perovskite solar cells (PSCs) is demonstrated by simply incorporating potassium ions. Experiments have shown the interstitial occupancy of potassium ions in the perovskite lattice and the formation of 2D K2PbI4 at the grain boundaries, both can reduce the trap density and inhibit ion migration, and thus suppress nonradiative recombination and photoinduced phase segregation. The average power conversion efficiency (PCE) of photovoltaic devices based on the perovskite with 40% Br is improved from 15.28% to 17.94%, among which the champion efficiency is 18.38% with an optimal 15% KI incorporation. Importantly, the champion open‐circuit voltage (Voc) remains unchanged (≈1.25 V) even when the bandgap reduces from 1.80 to 1.75 eV due to KI doping, effectively reducing the Voc deficit. In addition, the unencapsulated cells can sustain 94% of the initial PCE after 2000 h of storage in ambient atmosphere, affirming their outstanding stability.