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Third-order interatomic force constants reveal that the anharmonicity and soft phonon modes, rooted in the nature of unconventional chemical bonds between the B-site metals and chalcogen atoms, lead to an ultralow lattice thermal conductivity in this family of materials. The combination of intrinsically low lattice thermal conductivity and high power factor has realized highly efficient n-type and p-type ABQ3 thermoelectric materials showing various anisotropic characteristics. Considering the thermal and moisture stability of chalcogen