Methylammonium Cation Dynamics in Methylammonium Lead Halide Perovskites: A Solid-State NMR Perspective

In light of the intense recent interest in the methylammonium lead halides, CH₃NH₃PbX₃ (X = Cl, Br, and I) as sensitizers for photovoltaic cells, the dynamics of the methylammonium (MA) cation in these perovskite salts has been reinvestigated as a function of temperature via ²H, ¹⁴N, and ²⁰⁷Pb NMR spectroscopy. In the cubic phase of all three salts, the MA cation undergoes pseudoisotropic tumbling (picosecond time scale). For example, the correlation time, τ₂, for the C-N axis of the iodide salt is 0.85 ± 0.30 ps at 330 K. The dynamics of the MA cation are essentially continuous across the cubic ↔ tetragonal phase transition; however, ²H and ¹⁴N NMR line shapes indicate that subtle ordering of the MA cation occurs in the tetragonal phase. The temperature dependence of the cation ordering is rationalized using a six-site model, with two equivalent sites along the c-axis and four equivalent sites either perpendicular or approximately perpendicular to this axis. As the cubic ↔ tetragonal phase transition temperature is approached, the six sites are nearly equally populated. Below the tetragonal ↔ orthorhombic phase transition, ²H NMR line shapes indicate that the C-N axis is essentially frozen.