Structural Features and Optical Properties of All-Inorganic Zero-Dimensional Halides Cs4PbBr6-xIx Obtained by Mechanochemistry.

Despite the great success of hybrid CH3NH3PbI3 perovskite in photovoltaics, ascribed to its excellent optical absorption properties, its instability toward moisture is still an insurmountable drawback. All-inorganic perovskites are much less sensitive to humidity and have potential interest for solar cell applications. Alternative strategies have been developed to design novel materials with appealing properties, which include different topologies for the octahedral arrangements from three-dimensional (3D, e.g., CsPbBr3 perovskite) or two-dimensional (2D, e.g., CsPb2Br5) to zero-dimensional (0D, i.e., without connection between octahedra), as the case of Cs4PbX6 (X = Br, I) halides. The crystal structure of these materials is complex, and their thermal evolution is unexplored. In this work, we describe the synthesis of Cs4PbBr6-xIx (x = 0, 2, 4, 6) halides by mechanochemical procedures with green credentials; these specimens display excellent crystallinity enabling a detailed structural investigation from synchrotron X-ray powder diffraction (SXRD) data, essential to revisit some features in the temperature range of 90-298 K. In all this regime, the structure is defined in the trigonal R3̅c space group (#167). The presence of Cs and X vacancies suggests some ionic mobility into the crystal structure of these 0D halides. Bond valence maps (BVMs) are useful in determining isovalent surfaces for both Cs4PbBr6 and Cs4PbI6 phases, unveiling the likely ionic pathways for cesium and bromide ions and showing a full 3D connection in the bromide phase, in contrast to the iodide one. On the other hand, the evolution of the anisotropic displacement parameters is useful to evaluate the Debye temperatures, confirming that Cs atoms have more freedom to move, while Pb is more confined at its site, likely due to a higher covalency degree in Pb-X bonds than that in Cs-X bonds. Diffuse reflectance ultraviolet-visible (UV-vis) spectroscopy shows that the optical band gap can be tuned depending on iodine content (x) in the range of 3.6-3.06 eV. From density functional theory (DFT) simulations, the general trend of reducing the band gap when Br is replaced by I is well reproduced.

Crystal structure thermal evolution and novel orthorhombic phase of methylammonium lead bromide, CH3NH3PbBr3.

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[Formula: see text]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.

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.

Enhanced stability in CH3NH3PbI3 hybrid perovskite from mechano-chemical synthesis: structural, microstructural and optoelectronic characterization.

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.

Crystal Structure Features of CsPbBr3 Perovskite Prepared by Mechanochemical Synthesis.

We present a mechanochemical procedure, with solvent-free, green-chemistry credentials, to grow all-inorganic CsPbBr3 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.