Phononic Structure Engineering: the Realization of Einstein Rattling in Calcium Cobaltate for the Suppression of Thermal Conductivity

Phonons in condensed matter materials transmit energy through atomic lattices as coherent vibrational waves. Like electronic and photonic properties, an improved understanding of phononic properties is essential for the development of functional materials, including thermoelectric materials. Recently, an Einstein rattling mode was found in thermoelectric material Na0.8CoO2, due to the large displacement of Na between the [CoO₂] layers. In this work, we have realized a different type of rattler in another thermoelectric material Ca₃Co₄O₉ by chemical doping, which possesses the same [CoO₂] layer as Na_0.8CoO₂. It remarkably suppressed the thermal conductivity while enhancing its electrical conductivity. This new type of rattler was investigated by inelastic neutron scattering experiments in conjunction with ab-initio molecular dynamics simulations. We found that the large mass of dopant rather than the large displacement is responsible for such rattling in present study, which is fundamentally di erent from skutterudites, clathrates as well as Na analogue. We have also tentatively studied the phonon band structure of this material by DFT lattice dynamics simulation, showing the relative contribution to phonons in the distinct layers of Ca₃Co₄O₉.