Inverted (pin) perovskite solar cells (PSCs) afford improved operating stability in comparison to their nip counterparts but have lagged in power conversion efficiency (PCE). The energetic losses responsible for this PCE deficit in pin PSCs occur primarily at the interfaces between the perovskite and the charge-transport layers. Additive and surface treatments that use passivating ligands usually bind to a single active binding site: This dense packing of electrically resistive passivants perpendicular to the surface may limit the fill factor in pin PSCs. We identified ligands that bind two neighboring lead(II) ion (Pb ²⁺ ) defect sites in a planar ligand orientation on the perovskite. We fabricated pin PSCs and report a certified quasi–steady state PCE of 26.15 and 24.74% for 0.05– and 1.04–square centimeter illuminated areas, respectively. The devices retain 95% of their initial PCE after 1200 hours of continuous 1 sun maximum power point operation at 65°C.

Compared with the n-i-p structure, inverted (p-i-n) perovskite solar cells (PSCs) promise increased operating stability, but these photovoltaic cells often exhibit lower power conversion efficiencies (PCEs) because of nonradiative recombination losses, particularly at the perovskite/C ₆₀ interface. We passivated surface defects and enabled reflection of minority carriers from the interface into the bulk using two types of functional molecules. We used sulfur-modified methylthio molecules to passivate surface defects and suppress recombination through strong coordination and hydrogen bonding, along with diammonium molecules to repel minority carriers and reduce contact-induced interface recombination achieved through field-effect passivation. This approach led to a fivefold longer carrier lifetime and one-third the photoluminescence quantum yield loss and enabled a certified quasi-steady-state PCE of 25.1% for inverted PSCs with stable operation at 65°C for >2000 hours in ambient air. We also fabricated monolithic all-perovskite tandem solar cells with 28.1% PCE.

Lewis base molecules that bind undercoordinated lead atoms at interfaces and grain boundaries (GBs) are known to enhance the durability of metal halide perovskite solar cells (PSCs). Using density functional theory calculations, we found that phosphine-containing molecules have the strongest binding energy among members of a library of Lewis base molecules studied herein. Experimentally, we found that the best inverted PSC treated with 1,3-bis(diphenylphosphino)propane (DPPP), a diphosphine Lewis base that passivates, binds, and bridges interfaces and GBs, retained a power conversion efficiency (PCE) slightly higher than its initial PCE of ~23% after continuous operation under simulated AM1.5 illumination at the maximum power point and at ~40°C for >3500 hours. DPPP-treated devices showed a similar increase in PCE after being kept under open-circuit conditions at 85°C for >1500 hours.