Inverted perovskite solar cells face performance limitations due to non-radiative recombination at the perovskite surfaces in devices, including functional layers. Advanced characterization and density functional theory reveal that phosphonic acids passivate perovskite surface defects, while piperazinium chloride mitigates interface recombination by improving energy level alignment, introducing a field effect, and homogenizing the surface. Together, the quasi-Fermi level splitting of the perovskite is homogeneously increased by ca. 100mV. This enables two-terminal perovskite-on-silicon tandems to achieve a certified open-circuit voltage of 2V for a 1 cm² device and high performance in excess of 31%. The scalability of the passivation is furthermore demonstrated with homogenously passivated devices reaching certified efficiencies of 28.9% for an active area of 60 cm²