Phonon anharmonicity and soft-phonon mediated structural phase transition in $Cs_3Bi_2Br_9$

Abstract

We have carried out temperature-dependent x-ray diffraction and Raman scattering experiments on powder $Cs_3Bi_2Br_9$. Trigonal to monoclinic structural transition at around 95 K is discussed and shown to be driven by the softening of the soft mode. We propose a model to describe the dynamics of the incomplete soft-mode. Raman scattering experiments demonstrate the origin of the soft mode to the rocking motions of Br atoms that participate to form $BiBr_6$ octahedra, which correlates the reported theoretical calculations. Some of the Raman mode frequencies exhibit anomalous temperature dependence due to strong anharmonic phonon-phonon coupling. Temperature-dependent x-ray diffraction analysis estimate the volume thermal expansion coefficient in trigonal phase to be $13.54\times10^{-5} K^{-1}$. In the trigonal phase, the broadening of the full width at half maximum (FWHM) with increase in temperature for $E_g$ and $A_{1g}$ modes is accompanied by decaying of one optical phonon into two acoustic phonons. The volume thermal expansion rather than anharmonic phonon-phonon interaction dominates the frequency shift for the Raman modes in trigonal phase. In the monoclinic phase, the strength of four phonon processes to the frequency shift and linewidth broadening is much smaller than that for three phonon processes for some of the modes. The observed temperature dependence of FWHM of certain Raman modes in both phases suggests unusual electron-phonon coupling in the crystal.