Pressure-Induced Structural and Optical Properties of Organometal Halide Perovskite-Based Formamidinium Lead Bromide

Organometal halide perovskites (OMHPs) are attracting an ever-growing scientific interest as photovoltaic materials with moderate cost and compelling properties. In this Letter, pressure-induced optical and structural changes of OMHP-based formamidinium lead bromide (FAPbBr₃) were systematically investigated. We studied the pressure dependence of optical absorption and photoluminescence, both of which showed piezochromism. Synchrotron X-ray diffraction indicated that FAPbBr₃ underwent two phase transitions and subsequent amorphization, leading directly to the bandgap evolution with redshift followed by blueshift during compression. Raman experiments illustrated the high pressure behavior of organic cation and the surrounding inorganic octahedra. Additionally, the effect of cation size and the different intermolecular interactions between organic cation and inorganic octahedra result in the fact that FAPbBr₃ is less compressible than the reported methylammonium lead bromide (MAPbBr₃). High pressure studies of the structural evolution and optical properties of OMHPs provide important clues in optimizing photovoltaic performance and help to design novel OMHPs with higher stimuli-resistant ability

Pressure-Induced Structural Evolution and Optical Properties of Metal-Halide Perovskite CsPbCl₃

Metal-halide perovskites have emerged as the most promising semiconductor materials for advanced photovoltaic and optoelectronic applications. Herein, we comprehensively investigate the optical response and structural evolution of metal-halide perovskite CsPbCl₃ (ABX₃) upon compression. Band gap realized a pronounced narrowing under mild pressure followed by a sharp increase, which could be ascribed to Pb–Cl bond contraction and inorganic framework distortion, respectively. The transformation of the crystal structure is confirmed and analyzed through in situ high-pressure X-ray diffraction and Raman experiments, consistent with the evolution of optical properties. Combining with the first-principles calculations, we understand the electronic band structure changes and phase transition mechanism, which are ascribed to severe PbCl₆ octahedral titling and twisting. Our results demonstrate that the high-pressure technique can be used as a practical tool to modify the optical properties of metal-halide perovskites and maps an innovative strategy for better photovoltaic and optoelectronic device design

Pressure-Induced Structural Evolution and Band Gap Shifts of Organometal Halide Perovskite-Based Methylammonium Lead Chloride

Organometal halide perovskites are promising materials for optoelectronic devices. Further development of these devices requires a deep understanding of their fundamental structure–property relationships. The effect of pressure on the structural evolution and band gap shifts of methylammonium lead chloride (MAPbCl₃) was investigated systematically. Synchrotron X-ray diffraction and Raman experiments provided structural information on the shrinkage, tilting distortion, and amorphization of the primitive cubic unit cell. In situ high pressure optical absorption and photoluminescence spectra manifested that the band gap of MAPbCl₃ could be fine-tuned to the ultraviolet region by pressure. The optical changes are correlated with pressure-induced structural evolution of MAPbCl₃, as evidenced by band gap shifts. Comparisons between Pb-hybrid perovskites and inorganic octahedra provided insights on the effects of halogens on pressure-induced transition sequences of these compounds. Our results improve the understanding of the structural and optical properties of organometal halide perovskites

Pressure-Tailored Band Gap Engineering and Structure Evolution of Cubic Cesium Lead Iodide Perovskite Nanocrystals

Metal halide perovskites (MHPs) have attracted increasing research attention given the ease of solution processability with excellent optical absorption and emission qualities. However, effective strategies for engineering the band gap of MHPs to satisfy the requirements of practical applications are difficult to develop. Cubic cesium lead iodide (α-CsPbI₃), a typical MHP with an ideal band gap of 1.73 eV, is an intriguing optoelectric material owing to the approaching Shockley–Queisser limit. Here, we carried out a combination of in situ photoluminescence, absorption, and angle-dispersive synchrotron X-ray diffraction spectra to investigate the pressure-induced optical and structural changes of α-CsPbI₃ nanocrystals (NCs). The α-CsPbI₃ NCs underwent a phase transition from cubic (α) to orthorhombic phase and subsequent amorphization upon further compression. The structural changes with octahedron distortion to accommodate the Jahn–Teller effect were strongly responsible for the optical variation with the increase of pressure. First-principles calculations reveal that the band-gap engineering is governed by orbital interactions within the inorganic Pb–I frame through the structural modification. Our high-pressure studies not only established structure–property relationships at the atomic scale of α-CsPbI₃ NCs, but also provided significant clues in optimizing photovoltaic performance, thus facilitating the design of novel MHPs with increased stimulus-resistant capability

Pressure Effects on Structure and Optical Properties in Cesium Lead Bromide Perovskite Nanocrystals

Metal halide perovskites (MHPs) are gaining increasing interest because of their extraordinary performance in optoelectronic devices and solar cells. However, developing an effective strategy for achieving the band-gap engineering of MHPs that will satisfy the practical applications remains a great challenge. In this study, high pressure is introduced to tailor the optical and structural properties of MHP-based cesium lead bromide nanocrystals (CsPbBr₃ NCs), which exhibit excellent thermodynamic stability. Both the pressure-dependent steady-state photoluminescence and absorption spectra experience a stark discontinuity at ∼1.2 GPa, where an isostructural phase transformation regarding the <i>Pbnm</i> space group occurs. The physical origin points to the repulsive force impact due to the overlap between the valence electron charge clouds of neighboring layers. Simultaneous band-gap narrowing and carrier-lifetime prolongation of CsPbBr₃ trihalide perovskite NCs were also achieved as expected, which facilitates the broader solar spectrum absorption for photovoltaic applications. Note that the values of the phase change interval and band-gap red-shift of CsPbBr₃ nanowires are between those for CsPbBr₃ nanocubes and the corresponding bulk counterparts, which results from the unique geometrical morphology effect. First-principles calculations unravel that the band-gap engineering is governed by orbital interactions within the inorganic Pb–Br frame through structural modification. Changes of band structures are attributed to the synergistic effect of pressure-induced modulations of the Br–Pb bond length and Pb–Br–Pb bond angle for the PbBr₆ octahedral framework. Furthermore, the significant distortion of the lead–bromide octahedron to accommodate the Jahn–Teller effect at much higher pressure would eventually lead to a direct to indirect band-gap electronic transition. This study enables high pressure as a robust tool to control the structure and band gap of CsPbBr₃ NCs, thus providing insight into the microscopic physiochemical mechanism of these compressed MHP nanosystems