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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 Cu3Sb0.98Sn0.02Se4 sample was achieved at 1.05 at 623 K when the theoretical yield of a single synthesis was 10 mmol.
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