Realizing Enhanced Thermoelectric Performance and Hardness in Icosahedral Cu₅ FeS_4-x Se_x with High-Density Twin Boundaries

Bornite (Cu₅ FeS₄ ) is an Earth-abundant, nontoxic thermoelectric material. Herein, twin engineering and Se alloying are combined in order to further improve its thermoelectric performance. Cu₅ FeS_4-x Se_x (0 ≤ x ≤ 0.4) icosahedral nanoparticles, containing high-density twin boundaries, have been synthesized by a colloidal method. Spark plasma sintering retains twin boundaries in the pellets sintered from Cu₅ FeS_4-x Se_x colloidal powders. Thermoelectric property measurement demonstrates that alloying Se increases the carrier concentration, leading to much-improved power factor in Se-substituted Cu₅ FeS₄ , for example, 0.84 mW m^-1 K^-2 at 726 K for Cu₅ FeS_3.6 Se_0.4 ; low lattice thermal conductivity is also achieved, due to intrinsic structural complexity, distorted crystal structure, and existing twin boundaries and point defects. As a result, a maximum zT of 0.75 is attained for Cu₅ FeS_3.6 Se_0.4 at 726 K, which is about 23% higher than that of Cu₅ FeS₄ and compares favorably to that of reported Cu₅ FeS₄ -based materials. In addition, the Cu₅ FeS_4-x Se_x samples containing twin boundaries also obtain improved hardness compared to the ones fabricated by melting-annealing or ball milling. This work demonstrates an effective twin engineering-composition tuning strategy toward enhanced thermoelectric and mechanical properties of Cu₅ FeS₄ -based materials.