Migration of Constituent Protons in Hybrid Organic-Inorganic Perovskite Triggers Intrinsic Doping

The crucial separation of photocarriers in solar cells can be efficiently driven by contacting semiconductor phases with differing doping levels. Here we show that intrinsic doping surges in methylammonium lead iodide (MAPbI(3)) crystals as a response to environmental basicity. MAPbI(3) crystals were passivated with polybases to induce the deprotonation of its methyl ammonium ions (MA(+)). Stable crystals showed marked increases in photoluminescence and radiative decay, attributed to the presence of unbalanced charges acting as doped carriers. This emulates in a controlled manner the proton-withdrawing conditions of polycrystalline films, where excess basic precursors are found between grains. Raman spectroscopy showed the collective alignment of MA' cations within the intrinsically doped lattices, thus revealing the buildup of electric fields. On this basis, we propose a mechanism for the formation of doping gradients toward grain boundaries, potentially explaining the extended photocarrier lifetimes and diffusion lengths observed in perovskite solar cells.