We present a mechanochemical procedure, with solvent-free, greenchemistry credentials, to grow all-inorganic CsPbBr 3 perovskite. The crystal structure of this perovskite and its correlations with the physicochemical properties have been studied. Synchrotron X-ray diffraction (SXRD) and neutron powder diffraction (NPD) allowed us to follow the crystallographic behavior from 4 to 773 K. Unreported features like the observed negative thermal expansion of the b unit-cell parameter stem from octahedral distortions in the 4−100 K temperature range. The mechanochemical synthesis was designed to reduce the impact energy during the milling process, leading to a defect-free, well-crystallized sample characterized by a minimum unit-cell volume and octahedral tilting angles in the low-temperature orthorhombic perovskite framework, defined in the Pbnm space group. The UV−vis diffuse reflectance spectrum shows a reduced band gap of 2.22(3) eV, and the photocurrent characterization in a photodetector reveals excellent properties with potential applications of this material in optoelectronic devices.

Direct bandgap semiconductors of the hybrid-perovskite family CH3NH3PbX3 (X= I, Br, Cl) exhibit outstanding light absorption properties and are the materials of choice for solar energy applications. As an alternative...

Methylammonium (MA) lead trihalide perovskites, CH3NH3PbX3 (X = I, Br, Cl), have emerged as a new class of light-absorbing materials for photovoltaic applications, reaching efficiencies of 23% when implemented in solar cell heterojunctions. In particular, MAPbBr3 is a promising member with a large bandgap that gives rise to a high open circuit voltage. Here we present a structural study from neutron diffraction (ND) data of an undeuterated MAPbBr3 specimen, carried out to follow its crystallographic behaviour in the 2–298 K temperature range. Besides the known crystallographic phases, i.e. the high-temperature Pm$$\overline{3}$$ 3 ¯ m cubic structure, the intermediate I4/mcm tetragonal symmetry and the low-temperature Pnma orthorhombic phase, we additionally identified, from a detailed sequential ND analysis, a novel intermediate phase within the 148.5–154.0 K temperature range as an orthorhombic Imma structure, early associated with a coexistence of phases. Moreover, our ND data allowed us to unveil the configuration of the organic MA units and their complete localization within the mentioned temperature range, thus improving the crystallographic description of this compound. The evolution with temperature of the H-bonds between the organic molecule and the inorganic cage is also followed. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage seems essential to establish structure–property correlations that may drive further improvements.

All-inorganic lead halide perovskites like CsPbBr 3 , CsPbI 3 , or RbPbI 3 are good replacements for the classical hybrid organic–inorganic perovskites like CH 3 NH 3 PbI 3 , 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 RbPbI 3 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 PbI 6 octahedra. The lone electron pairs of Pb 2+ ions have a strong stereochemical effect on the PbI 6 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.

Among the hybrid organic–inorganic perovskites MAPbX3 (MA: methyl-ammonium CH3–NH3+, X = halogen), the triiodide specimen (MAPbI3) is still the material of choice for solar energy applications. Although it is able to absorb light above its 1.6 eV bandgap, its poor stability in humid air atmosphere has been a major drawback for its use in solar cells. However, we discovered that this perovskite can be prepared by ball milling in a straightforward way, yielding specimens with a superior stability. This fact allowed us to take atomic-resolution STEM images for the first time, with sufficient quality to unveil microscopic aspects of this material. We demonstrated full Iodine content, which might be related to the enhanced stability, in a more compact PbI6 framework with reduced unit-cell volume. A structural investigation from neutron powder diffraction (NPD) data of an undeuterated specimen was essential to determine the configuration of the organic MA unit in the 100–298 K temperature range. A phase transition is identified, from the tetragonal structure observed at RT (space group I4/mcm) to an orthorhombic (space group Pnma) phase where the methyl-ammonium organic units are fully localized. Our NPD data reveal that the MA changes are gradual and start before reaching the phase transition. Optoelectronic measurements yield a photocurrent peak at an illumination wavelength of 820 nm, which is redshifted by 30 nm with respect to previously reported measurements on MAPbI3 perovskites synthesized by crystallization from organic solvents.

Rubidium di-lead pentabromide, RbPb2Br5, belongs to a family of layered lead-containing halides, with the common formula APb2X5 (where A = K, Rb, Cs; X = Cl, Br). The optical properties...

A structural study from synchrotron X-ray and neutron diffraction of an undeuterated FAPbBr3 specimen allows identification of two phase transitions (Pm3̄m→P4/mbm→Pnma). Further rearrangements in the H bonds to Br imply thermal events observed by calorimetric measurements.

Two-dimensional (2D) layered metal halide perovskites have recently received a lot of attention due to their possible applications as photovoltaic and optoelectronic materials. Rubidium di-tin pentabromide, RbSn2Br5, is a promising...