Effects of Ni Doping on Thermoelectric Properties of Chalcopyrite

Chalcopyrite (CuFeS₂) has attracted interest as a thermoelectric material due to its narrow bandgap and its ability to tailor its carrier concentration through doping. In this study, we investigated the effects of Ni²⁺ substitution at Cu⁺ sites in chalcopyrite (Cu_1-xNi_xFeS₂) on its structural, microstructural, and thermoelectric properties. Samples were synthesized using mechanical alloying followed by hot pressing to ensure high-density compaction. X-ray diffraction analysis confirmed the formation of the tetragonal chalcopyrite phase without detectable secondary phases. The observed reduction in lattice parameters with increasing Ni content provided evidence of successful Ni incorporation at Cu sites within the chalcopyrite structure. Microstructural analysis and elemental mapping further supported the uniform distribution of Ni within the chalcopyrite matrix. Thermoelectric property measurements revealed that Ni-doped chalcopyrite exhibited n-type conduction. As the Ni concentration increased, the carrier concentration and electrical conductivity increased significantly, with Cu_0.92Ni_0.08FeS₂ achieving the highest electrical conductivity of 2.5 × 10⁴ Sm^-1 at 723 K. However, the absolute value of the Seebeck coefficient decreased with increasing Ni doping, following the expected trade-off between electrical conductivity and thermopower. The optimized composition, Cu_0.96Ni_0.04FeS₂, exhibited the highest thermoelectric performance, with a power factor of 0.50 mWm^-1K^-2 and a maximum dimensionless figure of merit (ZT) of 0.18 at 623 K. Compared to undoped chalcopyrite, these enhancements represent a 43% increase in power factor and a 50% improvement in ZT.