Detailed Structural Features of the Perovskite-Related Halide RbPbI₃ for Solar Cell Applications

All-inorganic lead halide perovskites like CsPbBr₃, CsPbI₃, or RbPbI₃ are good replacements for the classical hybrid organic-inorganic perovskites like CH₃NH₃PbI₃, susceptible to fast degradation in the presence of humid air. They also exhibit outstanding light absorption properties suitable for solar energy applications. Here, we describe the synthesis of RbPbI₃ by mechanochemical procedures with green credentials, avoiding toxic or expensive organic solvents; this specimen exhibits excellent crystallinity. We report neutron powder diffraction data, essential to revisit some subtle structural features around room temperature (200-400 K). In all these regimes, the orthorhombic Pnma crystal structure is characterized by the presence along the b direction of the crystal of double rows of edge-sharing PbI₆ octahedra. The lone electron pairs of Pb²⁺ ions have a strong stereochemical effect on the PbI₆ octahedral distortion. The relative covalency of Rb-I versus Pb-I bonds shows that the Pb-I-related motions are more rigid than Rb-I-related vibrations, as seen in the Debye temperatures from the evolution of the anisotropic displacements. The optical gap, measured by diffuse reflectance UV-vis spectroscopy, is ∼2.51 eV and agrees well with ab initio calculations. The thermoelectric Seebeck coefficient is 3 orders of magnitude larger than that of other halide perovskites, with a value of ∼117,000 μV·K^-1 at 460 K.