RESUMEN
Hybrid organic-inorganic lead halide perovskites (LHPs) have emerged as a highly significant class of materials due to their tunable and adaptable properties, which make them suitable for a wide range of applications. One of the strategies for tuning and optimizing LHP-based devices is the substitution of cations and/or anions in LHPs. The impact of Cs substitution at the A site on the structural, vibrational, and elastic properties of MAxCs1-xPbCl3-mixed single crystals was investigated using X-ray diffraction (XRD) and Raman and Brillouin light scattering techniques. The XRD results confirmed the successful synthesis of impurity-free single crystals, which exhibited a phase coexistence of dominant cubic and minor orthorhombic symmetries. Raman spectroscopy was used to analyze the vibrational modes associated with the PbCl6 octahedra and the A-site cation movements, thereby revealing the influence of cesium incorporation on the lattice dynamics. Brillouin spectroscopy was employed to investigate the changes in elastic properties resulting from the Cs substitution. The incorporation of Cs cations induced lattice distortions within the inorganic framework, disrupting the hydrogen bonding between the MA cations and PbCl6 octahedra, which in turn affected the elastic constants and the sound velocities. The substitution of the MA cations with smaller Cs cations resulted in a stiffer lattice structure, with the two elastic constants increasing up to a Cs content of 30%. The current findings facilitate a fundamental understanding of mixed lead chloride perovskite materials, providing valuable insights into their structural and vibrational properties.
RESUMEN
The relationship between halogen content and the elastic/vibrational properties of MAPbBr3-xClx mixed crystals (x = 1.5, 2, 2.5, and 3) with MA = CH3NH3+ has been studied using Brillouin and Raman spectroscopy at room temperature. The longitudinal and transverse sound velocities, the absorption coefficients and the two elastic constants C11 and C44 could be obtained and compared for the four mixed-halide perovskites. In particular, the elastic constants of the mixed crystals have been determined for the first time. A quasi-linear increase in the sound velocity and the elastic constant C11 with increasing chlorine content was observed for the longitudinal acoustic waves. C44 was insensitive to the Cl content and very low, indicating a low elasticity to shear stress in mixed perovskites regardless of the Cl content. The acoustic absorption of the LA mode increased with increasing heterogeneity in the mixed system, especially for the intermediate composition where the Br and Cl ratio was 1:1. In addition, a significant decrease in the Raman-mode frequency of the low-frequency lattice modes and the rotational and torsional modes of the MA cations was observed with decreasing Cl content. It clearly showed that the changes in the elastic properties as the halide composition changes were correlated with the lattice vibrations. The present findings may facilitate a deeper understanding of the complex interplay between halogen substitution, vibrational spectra and elastic properties, and may also pave the way for optimizing the operation of perovskite-based photovoltaic and optoelectronic devices by tailoring their chemical composition.
