Structure Evolution and Bonding Inhomogeneity toward High Thermoelectric Performance in Cu₂CoSnS_4-Se Materials

Lightweight diamond-like structure (DLS) materials are excellent candidates for thermoelectric (TE) applications due to their low costs, eco-friendly nature, and property stability. The main obstacles restricting the energy-conversion performance by the lightweight DLS materials are high lattice thermal conductivity and relatively low carrier mobility. By investigating the anion substitution effect on the structural, microstructural, electronic, and thermal properties of Cu₂CoSnS_4-Se, we show that the simultaneous enhancement of the crystal symmetry and bonding inhomogeneity engineering are effective approaches to enhance the TE performance in lightweight DLS materials. Particularly, the increase of x in Cu₂CoSnS_4-Se makes the DLS structure with the ideal tetrahedral bond angles of 109.5° favorable, leading to better crystal symmetry and higher carrier mobility in samples with higher selenium content. In turn, the phonon transport in the investigated DLS materials is strongly disturbed due to the bonding inhomogeneity between anions and three sorts of cations inducing large lattice anharmonicity. The increase of Se content in Cu₂CoSnS_4-Se only intensified this effect resulting in a lower lattice component of the thermal conductivity (κ_L) for Se-rich samples. As a result of the enhanced power factor S²ρ^-1 and the low κ_L, the dimensionless thermoelectric figure of merit ZT achieves a high value of 0.75 for Cu₂CoSnSe₄ DLS material. This work demonstrates that crystal symmetry and bonding inhomogeneity play an important role in the transport properties of DLS materials and provide a path for the development of new perspective materials for TE energy conversion.