CuGaTe₂ is p-type thermoelectric material with high thermoelectric potential. However, its performance is hindered by its intrinsic high resistivity and thermal conductivity. In this study, a synergistic strategy combining band engineering and chemical bonding modulation is employed to simultaneously optimize the electrical and thermal transport properties of CuGaTe₂. First-principles calculations reveal that Cd preferentially occupy Ga sites, leading to bandgap narrowing and increasing density of states near Fermi level. Consequently, both carrier concentration and density-of-states effective mass are simultaneously optimized, ultimately power factor reaches 1359 μW·m⁻¹·K⁻². Phonon dispersion analysis reveals that Cd doping induces acoustic-optical phonon avoided crossing behavior, decelerating phonon velocity. Combined with the increase of Grüneisen parameter and weakened chemical bonding, which significantly enhances lattice anharmonicity, leading to effectively reduce in lattice thermal conductivity. Microstructural characterization further reveals that CdTe doping leads to the formation of three-dimensional defect network consisting of point defects, dislocations, and stacking faults enhances phonon scattering. Ultimately, lattice thermal conductivity of doped sample is reduced to 0.81 W·m⁻¹·K⁻¹. Consequently, (CuGaTe₂)_0.9975(2CdTe)_0.0025 sample achieves enhanced zT of 1.05 at 823 K. This work provides insights into the synergistic effects of band engineering and chemical bonding modulation, offering pathway for the design of thermoelectric materials.

Cu₃SbSe₄, a copper-based sulfide free of rare earth elements, has received extensive attention in thermoelectric materials. However, its low carrier concentration restricts its widespread application. In this study, a microwave-assisted solution synthesis method was used to produce samples of Cu₃SbSe₄, which enabled the formation of CuSe in situ and increased the yield. Through the use of first-principles calculations, structural analysis, and performance evaluation, it was found that CuSe can enhance the carrier concentration and that induced nano-defects have a positive effect on reducing the lattice thermal conductivity. Moreover, doping with Sn decreases the band gap of the system and moves the Fermi level into the valence band, increasing the carrier concentration to 1.15 × 10⁻²⁰ cm⁻³. Finally, the zT value of the Cu₃Sb_0.98Sn_0.02Se₄ sample was achieved at 1.05 at 623 K when the theoretical yield of a single synthesis was 10 mmol.

The previous works commonly adjust the carrier concentration through acceptor doping, but at the same time, the decrease of the Seebeck coefficient limits the further improvement of electrical properties in Cu₃SbSe₄-based materials. In this work, a microwave-assisted hydrothermal synthesis method was used to synthesize Cu₃SbSe₄/TiO₂ hollow microspheres. Part of TiO₂ participates in the reaction, replaces the Sb site of Cu₃SbSe₄ to form holes, and the rest is dispersed in the matrix in the form of the second phase. The first-principles calculations reveal that the doping of Ti significantly changes the band structure and phonon spectrum, thereby regulating carrier concentration while increasing phonon scattering. In addition, experimental results show that the energy filtering effect generated by the extra-mixed TiO₂ nano particles, which suppresses the decrease of Seebeck coefficient by acceptor doping. Consequently, the highest average power factor 897.5 μW m⁻¹ K⁻² and the zT peak value of 0.70 can be obtained in Cu₃SbSe₄/6%TiO₂ sample at 298–623 K. This work provides a new sight to improve the thermoelectric properties in Cu₃SbSe₄ through carrier concentration regulation and nano-phase composition.