Structure-Band Gap Relationships in Hexagonal Polytypes and Low-Dimensional Structures of Hybrid Tin Iodide...

The present study deals with the structural characterization and classification of the novel compounds 1-8 into perovskite subclasses and proceeds in extracting the structure-band gap relationships between them. The compounds were obtained from the employment of small, 3-5-atom-wide organic ammonium ions seeking to discover new perovskite-like compounds. The compounds reported here adopt unique or rare structure types akin to the prototype structure perovskite. When trimethylammonium (TMA) was employed, we obtained TMASnI₃ (1), which is our reference compound for a "perovskitoid" structure of face-sharing octahedra. The compounds EASnI₃ (2b), GASnI₃ (3a), ACASnI₃ (4), and IMSnI₃ (5) obtained from the use of ethylammonium (EA), guanidinium (GA), acetamidinium (ACA), and imidazolium (IM) cations, respectively, represent the first entries of the so-called "hexagonal perovskite polytypes" in the hybrid halide perovskite library. The hexagonal perovskites define a new family of hybrid halide perovskites with a crystal structure that emerges from a blend of corner- and face-sharing octahedral connections in various proportions. The small organic cations can also stabilize a second structural type characterized by a crystal lattice with reduced dimensionality. These compounds include the two-dimensional (2D) perovskites GA₂SnI₄ (3b) and IPA₃Sn₂I₇ (6b) and the one-dimensional (1D) perovskite IPA₃SnI₅ (6a). The known 2D perovskite BA₂MASn₂I₇ (7) and the related all-inorganic 1D perovskite "RbSnF₂I" (8) have also been synthesized. All compounds have been identified as medium-to-wide-band-gap semiconductors in the range of E_g = 1.90-2.40 eV, with the band gap progressively decreasing with increased corner-sharing functionality and increased torsion angle in the octahedral connectivity.