Light-Induced Metallic and Paramagnetic Defects in Halide Perovskites from Magnetic Resonance

Abstract

Halide perovskites are promising next-generation solar cell materials, but their commercialization is hampered by their propensity to degrade under operating conditions, particularly under heat, humidity, and light. Identifying degradation products and linking them to the degradation mechanism at the atomic scale is necessary to design more stable perovskite materials. Here we use magnetic resonance methods to identify and characterize the formation of both metallic lead clusters and Pb³⁺ defects upon light-induced degradation of methylammonium lead halide perovskite using nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) measurements. Paramagnetic relaxation enhancement (PRE) of the ¹H NMR resonances demonstrates the presence of localized paramagnetic Pb³⁺ defects, a large Knight shift of the ²⁰⁷Pb NMR proves the presence of lead metal, and their relative proportions are determined by the differing temperature dependence in variable-temperature EPR. This work reconciles previous conflicting literature results, enabling the use of EPR spectroscopy to monitor photodegradation of perovskite devices.