NMR spectroscopy probes microstructure, dynamics and doping of metal halide perovskites

Solid-state magic-angle spinning NMR spectroscopy is a powerful technique to probe atomic-level microstructure and structural dynamics in metal halide perovskites. It can be used to measure dopant incorporation, phase segregation, halide mixing, decomposition pathways, passivation mechanisms, short-range and long-range dynamics, and other local properties. This Review describes practical aspects of recording solid-state NMR data on halide perovskites and how these afford unique insights into new compositions, dopants and passivation agents. We discuss the applicability, feasibility and limitations of ¹H, ¹³C, ¹⁵N, ¹⁴N, ¹³³Cs, ⁸⁷Rb, ³⁹K, ²⁰⁷Pb, ¹¹⁹Sn, ¹¹³Cd, ²⁰⁹Bi, ¹¹⁵In, ¹⁹F and ²H NMR in typical experimental scenarios. We highlight the pivotal complementary role of solid-state mechanosynthesis, which enables highly sensitive NMR studies by providing large quantities of high-purity materials of arbitrary complexity and of chemical shifts calculated using density functional theory. We examine the broader impact of solid-state NMR on materials research and how its evolution over seven decades has benefitted structural studies of contemporary materials such as halide perovskites. Finally, we summarize some of the open questions in perovskite optoelectronics that could be addressed using solid-state NMR. We, thereby, hope to stimulate wider use of this technique in materials and optoelectronics research.