Glass-like Transport Dominates Ultralow Lattice Thermal Conductivity in Modular Crystalline Bi₄O₄SeCl₂.

Abstract

Crystalline Bi₄O₄SeCl₂ exhibits record-low 0.1 W/mK lattice thermal conductivity (κ_<i>L</i>), but the underlying transport mechanism is not yet understood. Using a theoretical framework which incorporates first-principles anharmonic lattice dynamics into a unified heat transport theory, we compute both the particle-like and glass-like components of κ_<i>L</i> in crystalline and pellet Bi₄O₄SeCl₂ forms. The model includes intrinsic three- and four-phonon scattering processes and extrinsic defect and extended defect scattering contributing to the phonon lifetime, as well as temperature-dependent interatomic force constants linked to phonon frequency shifts and anharmonicity. Bi₄O₄SeCl₂ displays strongly anisotropic complex crystal behavior with dominant glass-like transport along the cross-plane direction. The uncovered origin of κ_<i>L</i> underscores an intrinsic approach for designing extremely low κ_<i>L</i> materials.