Anomalous Lattice Thermal Conductivity in Rocksalt IIA–VIA Compounds

Materials with an intrinsic (ultra)low lattice thermal conductivity (kL) are critically important for the development of efficient energy conversion devices. In the present work, we have investigated microscopic origins of low kL behavior in BaO, BaS, and MgTe by exploring lattice dynamics and phonon transport of 16 isostructural MX (M = Mg, Ca, Sr, and Ba and X = O, S, Se, and Te) compounds in the rocksalt (NaCl)-type structure. Anomalous trends are observed for kL in MX (M = Mg, Ca, Sr, and Ba and X = O, S, Se, and Te) compounds except for the MgX (X = O, S, Se, and Te) series in contrast to the expected trend from their atomic mass. The underlying mechanisms for such low kL behavior in large mismatch atomic mass systems, namely, BaO, BaS, and MgTe, are thoroughly analyzed. We propose the following factors that might be responsible for low kL behavior in these materials: (1) high mass contrast provides a phonon gap between the acoustic and optic branches; (2) softening of transverse acoustic (TA) phonon modes due to the presence of heavy element; (3) low-lying optic (LLO) phonon modes fall into the acoustic mode region and are responsible for softening of the acoustic phonon modes or enhancing the overlap between LLO (TO) and longitudinal acoustic (LA) phonon modes, thereby increasing scattering rates; (4) shorter phonon lifetimes; and (5) a relatively high density (ρ) and a large Grüneisen parameter (γ) leads to strong anharmonicity. Moreover, tensile strain causes a further reduction in kL for BaO, BaS, and MgTe through phonon softening and near ferroelectric instability. Our comprehensive study on 16 binary MX (M = Mg, Ca, Sr, and Ba and X = O, S, Se, and Te) compounds provides a pathway for designing (ultra)low kL materials through phonon engineering even with simple crystal systems.