Why are Lead Iodide‐Based Perovskite Precursor Inks Yellow?

Abstract A challenge faced by metal halide perovskite (MHP) photovoltaics is scaling up solution deposition processes to realize rapid and inexpensive manufacturing. The challenge lies in completely understanding and controlling solution speciation, nucleation, and self‐assembly of iodoplumbate complexes during solvent evaporation as the liquid transforms into gels and solids. An accurate description of solution species, at all points in the transformation, is a prerequisite to design robust and reliable processes. Here, the common assumption that initial monoplumbate solution species typically invoked (e.g., [PbI ₆ ] ⁴⁻ ) are certainly not the origin of optical absorbance at >400 nm wavelengths is disproved, as are many large particles of common “intermediate” iodoplumbate phases with face‐ or edge‐sharing connectivity. Instead, a new perspective is offered, involving (partially) corner‐sharing iodo(poly)plumbates (>1 Pb ²⁺ per complex) that experience highly dynamic chemical environments. It is outlined how the MHP field would benefit by elucidating these phenomena. Future work is required to determine the size and kinetic behavior of polyplumbate species, and contextualize these findings in relation to broader trends in materials chemistry beyond MHPs. Ultimately, a complete explanation for the solution speciation, optical absorbance signatures, and the color of MHP precursor inks remains an open challenge to the community.