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.

Nickel phthalocyanine as a hole transporting material in inverted planar perovskite solar cells leads to a power conversion efficiency of 14.3%.

The high-efficiency photocarrier collection at the interfaces plays an important role in improving the performance of perovskite solar cells (PSCs) because the photocarrier effective diffusion lengths in the lead halide perovskite absorbers usually surpass the incident depths of light. Developing the electron selective layer (ESL) that has good interfaces with photoactive perovskite and current collector layer-like fluorine-doped tin oxide (FTO) is actively pursued. Here, an unusual dense film of faceted rutile TiO 2 single crystals with a gradient of the Sn 4+ dopant grown heteroepitaxially on the FTO layer is obtained by a hydrothermal route and subsequent thermal treatment. Owing to the global features including low concentration of defects, atomically smooth coherent interface with FTO, and gradient doping-induced built-in electric field to promote the collection of photoelectrons in it, an optimal PSC with such a film as the ESL exhibits an efficiency of 17.2% with an open-circuit voltage of 1.1 V and fill factor of 76.1%, which are among the highest values of the PSCs with rutile TiO 2 films as ESLs.