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In this work, we design and synthesize a hybrid structure consisting of Sn-incorporated Cu3SbSe4 and a second phase CuSe, that is, (Cu3Sb1 − xSnxSe4)(CuSe)y (x = 0–0.04, y = 0.3–0.08), and explore the role of each phase on the improvement of the thermoelectric (TE) performance. In the Cu3Sb1 − xSnxSe4 phase, the element Sn residing at the Sb site provides p-type holes while at the same time increasing the point defects and crystal structure distortion. The presence of the second phase CuSe, which is in situ formed within the Cu3Sb1 − xSnxSe4 matrix, not only improves the electrical conductivity but also increases the phonon scattering on the phase boundaries. As a result, the hybrid structure allows the improvement in TE performance with the highest ZT value of 0.37 at ∼600 K for the samples at x = 0.02–0.03 and y = 0.11–0.09, which is about 42% higher than that of pristine Cu3SbSe4. This work reveals us a new method of improving TE performance, that is, through organizing a hybrid structure in Cu3SbSe4-based composites. [ABSTRACT FROM AUTHOR]

AgBiSe2 is a promising thermoelectric (TE) candidate because of its intrinsically low thermal conductivity (κ = 0.4–0.5 W K−1 m−1 at ∼770 K) and optimal n-type carrier concentration (5.85 × 1018 cm−3 at 300 K). However, its TE figure of merit (ZT) is still low (0.3 at ∼770 K). Therefore, it is necessary to further improve its ZT. In this work, the solid solutions (AgBiSe2)1−x(Ag2Te)x (x = 0–0.125) have been designed through simple alloying Ag2Te inspired by the entropy engineering concept, and the TE performance has been further regulated. The analyses show that the exothermic effects related to α/β and β/γ phase transitions weaken, and the transition temperature of β/γ decreases as the Ag2Te content increases, which indicates the stabilization of the cubic γ-phase at high temperatures. Aside from that, the power factor (PF) enhances from 2.91 μW/cm K2 (x = 0) to 3.49 μW/cm K2 (x = 0.075), and at the same time, the lattice thermal conductivity reduces from 0.3 W K−1 m−1 to 0.1 W K−1 m−1 at ∼760 K. This directly improves the TE performance with the highest ZT value of 1.0, which is almost double that of the pristine AgBiSe2. The result suggests that the entropy engineering is a very effective screening method in thermoelectrics. [ABSTRACT FROM AUTHOR]