Cu3BiS3: Two‐Dimensional Coordination Induces Out‐of‐Plane Phonon Scattering Enabling Ultralow Thermal Conductivity

The discovery of compounds with low thermal conductivity and the understanding of their microscopic mechanisms are of great challenges and scientific significance. Herein, we report a unique ternary sulfide compound, Cu3BiS3, in which all Cu atoms are coordinated within a two‐dimensional [CuS3] triangle plane. This local coordination leads to efficient out‐of‐plane phonon scattering and an ultralow thermal conductivity. Through DFT phonon spectrum calculations and analyses, we reveal that the lowest vibration frequency decreases from 2 THz for high‐dimensional [CuS4] tetrahedral coordinated Cu atoms in CuBiS2 (CN=4, with an average Cu−S bond length of 2.328 Å) to 1.5 THz for low‐dimensional [CuS3] triangular coordinated Cu atoms in Cu3BiS3 (CN=3, with a shorter Cu−S bond length of 2.285 Å). This is due to the out‐of‐plane thermal vibration of the Cu atoms in the latter. Consequently,Cu3BiS3 exhibits one of the lowest values of κlat (0.32 W/m K) among its peer, with a 36 % reduction compared to CuBiS2 (0.50 W/m K). This groundbreaking discovery highlights the significant role of 2D local coordination in reducing thermal conductivity through characteristic out‐of‐plane phonon scattering, while also contributing to a large Grüneisen parameter (2.06) in Cu3BiS3. We report herein a groundbreaking discovery, thus highlighting the significant role of low‐dimensional local coordination ([CuS3] D3h triangle plane) in lowering the thermal conductivity through characteristic out‐of‐plane phonon scattering, while also contributing to a large Grüneisen parameter. This allows Cu3BiS3 to exhibit one of the lowest κlat values (0.32 W/m K) reported so far.