Dynamic Nuclear Polarization of Inorganic Halide Perovskites

The intrinsic low sensitivity of nuclear magnetic resonance (NMR) experiments limits their utility for structure determination of materials. Dynamic nuclear polarization (DNP) under magic angle spinning (MAS) has shown tremendous potential to overcome this key limitation, enabling the acquisition of highly selective and sensitive NMR spectra. However, so far, DNP methods have not been explored in the context of inorganic lead halide perovskites, which are a leading class of semiconductor materials for optoelectronic applications. In this work, we study cesium lead chloride and quantitatively compare DNP methods based on impregnation with a solution of organic biradicals with doping of high-spin metal ions (Mn²⁺) into the perovskite structure. We find that metal-ion DNP provides the highest bulk sensitivity in this case, while highly surface-selective NMR spectra can be acquired using impregnation DNP. The performance of both methods is explained in terms of the relaxation times, particle size, dopant concentration, and surface wettability. We envisage the future use of DNP NMR approaches in establishing structure-activity relationships in inorganic perovskites, especially for mass-limited samples such as thin films.