Local Structure in Crystalline, Glass and Melt States of a Hybrid Metal Halide Perovskite

The pursuit of structure-property relationships in crystalline metal halide perovskites (MHPs) has yielded an unprecedented combination of advantageous characteristics for wide-ranging optoelectronic applications. While crystalline MHP structures are readily accessible through diffraction-based structure refinements, providing a clear view of associated long-range ordering, the local structures in more recently discovered glassy MHP states remain unexplored. Herein, we utilize a combination of Raman spectroscopy, solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, in situ X-ray diffraction (XRD) and pair distribution function (PDF) analysis to investigate the coordination environment in crystalline, glass and melt states of the 2D MHP [(S)-(−)-1-(1-naphthyl)ethylammonium]₂PbBr₄. While crystalline SNPB shows polarization-dependent Raman spectra, the glassy and melt states exhibit broad features and lack polarization dependence. Solid-state NMR reveals disordering at the organic-inorganic interface of the glass due to significant spatial disruption in the tethering ammonium groups and the corresponding dihedral bond angles connecting the naphthyl and ammonium groups, while still preserving substantial naphthyl group registry and remnants of the layering from the crystalline state (deduced from XRD analysis). Moreover, PDF analysis demonstrates the persistence of corner-sharing PbBr₆ octahedra in the inorganic framework of the melt/glass phases, but with a loss of structural coherence over length scales exceeding approximately one octahedron due to disorder in the inter- and intraoctahedra bond angles/lengths. These findings deepen our understanding of diverse MHP structural motifs and how structural alterations within the MHP glass affect properties, offering potential for advancing next-generation phase change materials and devices.