s-d Coupling-Induced Dynamic Off-Centering of Cu Drives High Thermoelectric Performance in TlCuS

Seeking new and efficient thermoelectric materials requires a detailed comprehension of chemical bonding and structure in solids at microscopic levels, which dictates their intriguing physical and chemical properties. Herein, we investigate the influence of local structural distortion on the thermoelectric properties of TlCuS, a layered metal sulfide featuring edge-shared Cu-S tetrahedra within Cu2S2 layers. While powder X-ray diffraction suggests average crystallographic symmetry with no distortion in CuS4 tetrahedra, the synchrotron X-ray pair distribution function experiment exposes concealed local symmetry breaking, with dynamic off-centering distortions of the CuS4 tetrahedra. The Cu off-centering is driven by the on-site coupling of filled 3d and unoccupied 4s orbitals (s-d) of Cu through a second-order Jahn-Teller mechanism. Bond softening by the p-d* (S-3p and Cu-3d) antibonding interaction coupled with dynamic off-centering distortions causes significant anharmonicity in the lattice, which acts as a phonon-blocking mechanism conducive to ultralow lattice thermal conductivity (κlat) (∼0.35-0.23 W m-1 K-1 in the ∼296-573 K temperature range) in TlCuS. The synergy between low κlat and multiband electronic structure leads to thermoelectric figure-of-merits (zT) of ∼1 and ∼1.3 at 573 K for pristine TlCuS and TlCu0.98S, respectively, underscoring the potential of metal sulfides as promising high-performance thermoelectrics.