Untying the Cesium “Not”: Cesium–Iodoplumbate Complexation in Perovskite Solution-Processing Inks Has Implications for Crystallization

We illustrate the critical importance of the energetics of cation–solvent versus cation–iodoplumbate interactions in determining the stability of ABX3 perovskite precursors in a dimethylformamide (DMF) solvent medium. We have shown, through a complementary suite of nuclear magnetic resonance (NMR) and computational studies, that Cs+ exhibits significantly different solvent vs iodoplumbate interactions compared to organic A+-site cations such as CH3NH3 + (MA+). Two NMR studies were conducted: 133Cs NMR analysis shows that Cs+ and MA+ compete for coordination with PbI3 – in DMF. 207Pb NMR studies of PbI2 with cationic iodides show that perovskite-forming Cs+ (and, somewhat, Rb+) do not comport with the 207Pb chemical shift trend found for Li+, Na+, and K+. Three independent computational approaches (density functional theory (DFT), ab initio Molecular Dynamics (AIMD), and a polarizable force field within Molecular Dynamics) yielded strikingly similar results: Cs+ interacts more strongly with the PbI3 – iodoplumbate than does MA+ in a polar solvent environment like DMF. The stronger energy preference for PbI3 – coordination of Cs+ vs MA+ in DMF demonstrates that Cs+ is not simply a postcrystallization cation “fit” for the perovskite A+-site. Instead, it may facilitate preorganization of the framework precursor that eventually transforms into the crystalline perovskite structure.