Publication date: 17th February 2025
Solid state NMR spectroscopy has emerged as a powerful analytical tool for the investigation of advanced materials in the field of energy storage, nanotechnology, pharmaceuticals etc. Its utility spans widely in providing structural, dynamic and compositional aspects of materials at the atomic level which significantly contributes establishing a structure-function relationship. Recently, researchers in metal halide perovskites (MHP; 3D ABX3 structure; A+ = methylammonium, formamidinium, Cs+, Rb+; B2+ = Pb2+, Sn2+; X- = I-, Br-, Cl-) have shown substantial interest in so-called “pseudo-halides” (PHs).1 These anions (for example, HCOO-, CH2OHCOO-, BF4- etc.) have the capacity to either substitute directly for halides in the 3D MHP structure, or to bind to B2+ by occupying vacant X- sites. Halide defects (e.g. vacancies) in MHPs are particularly damaging to solar cell performance, and PHs have the capability to passivate these defect states. However, not much experimental work has been carried out to explore the changes in the local structure, interactions, the effect on the stability of MHPs as these PHs are added. These questions are important as they have significant implications on the device performances. Therefore, we address these questions using advanced solid state NMR techniques such as 127I NQR (Nuclear Quadrupolar Resonance spectroscopy). NQR is highly sensitive to the symmetry and the structural symmetry changes often cause line broadening effects, making it feasible to detect if the PHs interact with perovskite lattice. Further 1D 1H, 13C, 11B, 19F, 23Na NMR and 2-D 23Na-1H PRESTO experiments of the doped perovskites when compared to the pure PHs or the MHPs provide valuable insights to these questions.
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