Layered structures of organic/inorganic hybrid halide perovskites

Abstract: Organic-inorganic hybrid halide perovskites, in which the A cations of an ABX$_3$ perovskite are replaced by organic cations, may be used for photovoltaic and solar thermoelectric applications. In this contribution, we systematically study three lead-free hybrid perovskites, i.e., methylammonium tin iodide CH$_3$NH$_3$SnI$_3$, ammonium tin iodide NH$_4$SnI$_3$, and formamidnium tin iodide HC(NH$_2$)$_2$SnI$_3$, by first-principles calculations. We find that in addition to the commonly known motif in which the corner-shared SnI$_6$ octahedra form a three-dimensional network, these materials may also favor a two-dimensional (layered) motif formed by alternating layers of the SnI$_6$ octahedra and the organic cations. These two motifs are nearly equal in free energy and are separated by low barriers. These layered structures features many flat electronic bands near the band edges, making their electronic structures significantly different from those of the structural phases composed of three-dimension networks of SnI$_6$ octahedra. Furthermore, because the electronic structures of HC(NH$_2$)$_2$SnI$_3$ are found to be rather similar to those of CH$_3$NH$_3$SnI$_3$, formamidnium tin iodide may also be promising for the applications of methylammonium tin iodide.