Crystal and Electronic Structures of Complex Bismuth Iodides A3Bi2I9 (A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics

Abstract

Ternary bismuth halides form an interesting functional materials class in the context of the closely related Pb halide perovskite photovoltaics, especially given the significantly reduced toxicity of Bi when compared with Pb. The compounds A3Bi2I9 (A = K, Rb, Cs) examined here crystallize in two different structure types: the layered defect-perovskite K3Bi2I9 type, and the Cs3Cr2Cl9 type. The latter structure type features isolated Bi2I93– anions. Here, the crystal structures of the ternary iodides are redetermined and a corrected structural model for Rb3Bi2I9, as established by single crystal X-ray diffraction and solid state 87Rb NMR spectroscopy and supported by density functional theory (DFT) calculations is presented. A variety of facile preparation techniques for single crystals, bulk materials, as well as solution-processed thin films are described. The optical properties and electronic structures are investigated experimentally by optical absorption and ultraviolet photoemission spectroscopy and c...