The Role of Bulk and Interface Recombination in High‐Efficiency Low‐Dimensional Perovskite Solar Cells

2D Ruddlesden–Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite‐based cells. Herein, 2D (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)_n?1Pb_nI_3n+1 perovskite cells with different numbers of PbI₆]^4? sheets (n = 2–4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open‐circuit voltage (V_OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C₆₀ interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi‐Fermi level splitting matches the device V_OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.