Modulating Adsorption Orientation of Multi‐Site Ligand Enables Perovskite/Silicon Tandem Solar Cells with Voltage Exceeding 2 V

defects via coordination and hydrogen bonding, respectively, and incorporating a chlorine group promotes the parallel adsorption on the perovskite surface. The parallel configuration, rather than vertical orientation, minimizes the distance between the active site and the perovskite defects, significantly boosting passivation efficacy and mitigating the resistive barrier. Consequently, 1.67 eV bandgap perovskite solar cells achieve a power conversion efficiency (PCE) of 23.55%. Furthermore, integrating this cell into perovskite/silicon TSC yields a high voltage of over 2 volts and a PCE of 31.42% adopting a planar silicon sub-cell. Remarkably, encapsulated tandem devices retain over 80% of their initial PCE after 1960 h of maximum power point tracking under 1-sun illumination at 25 °C.