Structural Phase Transitions and Thermal Degradation Process of MAPbCl₃ Single Crystals Studied by Raman and...

Raman spectroscopy was applied to MAPbCl₃ single crystals in a wide frequency range from 10 to 3500 cm^-1 over a broad temperature range from -196 °C to 200 °C including both two structural phase transitions and a thermal degradation range. Low-frequency lattice modes of MAPbCl₃ were revealed for the first time, which showed discontinuous anomalies along with the change in the number of Raman modes at the transition points of -114 °C and -110 °C. Several Raman modes related to the C-N stretching and MA rocking modes in addition to the lattice modes displayed temperature dependences similar to those of MAPbBr₃ in both Raman shifts and half widths, indicating that the MA cation arrangement and H-halide bond interactions behave similarly in both systems during the phase transition. The substantial increase in the half widths of nearly all Raman modes especially suggests that the dynamic disorder caused by the free rotational motions of MA cations induces significant anharmonicity in the lattice and thus, reduces the phonon lifetimes. High-temperature Raman and Brillouin scattering measurements showed that the spectral features changed drastically at ~200 °C where the thermal decomposition of MAPbCl₃ into PbCl₂ began. This result exhibits that combined Raman and Brillouin spectroscopic techniques can be a useful tool in monitoring temperature-induced or temporal changes in lead-based halide perovskite materials.