Strong low-energy rattling modes enabled liquid-like ultralow thermal conductivity in a well-ordered solid

ABSTRACT Crystalline solids exhibiting inherently low lattice thermal conductivity (κL) are of great importance in applications such as thermoelectrics and thermal barrier coatings. However, κL cannot be arbitrarily low and is limited by the minimum thermal conductivity related to phonon dispersions. In this work, we report the liquid-like thermal transport in a well-ordered crystalline CsAg5Te3, which exhibits an extremely low κL value of ∼0.18 Wm−1K−1. On the basis of first-principles calculations and inelastic neutron scattering measurements, we find that there are lots of low-lying optical phonon modes at ∼3.1 meV hosting the avoided-crossing behavior with acoustic phonons. These strongly localized modes are accompanied by weakly bound rattling Ag atoms with thermally induced large amplitudes of vibrations. Using the two-channel model, we demonstrate that coupling of the particle-like phonon modes and the heat-carrying wave-like phonons is essential for understanding the low κL, which is heavily deviated from the 1/T temperature dependence of the standard Peierls theory. In addition, our analysis indicates that the soft structural framework with liquid-like motions of the fluctuating Ag atoms is the underlying cause that leads to the suppression of the heat conduction in CsAg5Te3. These factors synergistically account for the ultralow κL value. Our results demonstrate that the liquid-like heat transfer could indeed exist in a well-ordered crystal.