Resonant bonding leads to low lattice thermal conductivity

Understanding the lattice dynamics and low thermal conductivities of IV–VI, V[subscript 2]–VI[subscript 3] and V materials is critical to the development of better thermoelectric and phase-change materials. Here we provide a link between chemical bonding and low thermal conductivity. Our first-principles calculations reveal that long-ranged interaction along the 〈100〉 direction of the rocksalt structure exist in lead chalcogenides, SnTe, Bi[subscript 2]Te[subscript 3], Bi and Sb due to the resonant bonding that is common to all of them. This long-ranged interaction in lead chalcogenides and SnTe cause optical phonon softening, strong anharmonic scattering and large phase space for three-phonon scattering processes, which explain why rocksalt IV–VI compounds have much lower thermal conductivities than zincblende III–V compounds. The new insights on the relationship between resonant bonding and low thermal conductivity will help in the development of better thermoelectric and phase change materials.United States. Dept. of Energy. Office of Science (Award DE-SC0001299/DE-FG02-09ER46577)United States. Air Force Office of Scientific Research. Multidisciplinary University Research InitiativeSamsung (Firm) (Scholarship