Effects of Double Doping Germanium and Indium on the Thermoelectric Properties of Permingeatite

다국어 초록 (Multilingual Abstract)

Cu3Sb1–x–yGexInySe4 (0.02 ≤ x ≤ 0.12; 0.04 ≤ y ≤ 0.08) permingeatite compounds doped with Ge andIn were prepared using solid-state synthesis. The phases and microstructures were analyzed, and the chargetransport and thermoelectric properties were evaluated according to the Ge and In doping content. Most ofthe samples contained a single phase of permingeatite with a tetragonal structure; however, secondary phases(Cu0.875InSe2, In2Se3, and InSb) were detected in the samples with x = 0.12 and y = 0.08. Both the a-axis andc-axis lattice constants of permingeatite were increased by Ge and In doping, with a = 0.5651–0.5655 nm andc = 1.1249–1.1255 nm, but the change in lattice constant due to the change in doping amount wasinsignificant. The melting point of the sample double-doped with Ge and In was determined to be 736 K, whichwas lower than the melting point (741 K) of pure Cu3SbSe4. This lowering of the melting point was attributedto the formation of a solid solution. The electrical conductivity exhibited degenerate semiconductor behavior,decreasing with increasing temperature. As the Ge and In doping content increased, the carrier concentrationand electrical conductivity increased; however, when x ≥ 0.12, the electrical conductivity did not increasefurther. The Seebeck coefficient exhibited positive values and p-type conduction characteristics. In addition,intrinsic transitions did not occur in the measurement temperature range, and the Seebeck coefficientincreased as the doping level increased. The power factor exhibited a positive temperature dependence, andCu3Sb0.86Ge0.08In0.06Se4 exhibited the highest value of 0.89 mWm–1K–2 at 623 K. As the temperature increased,the thermal conductivity tended to decrease because of the decreased lattice thermal conductivity and slightlyincreased electronic thermal conductivity. All the samples exhibited minimum thermal conductivities of 0.94–1.11 Wm–1K–1 at 523 K. At high temperatures, the double doping of Ge and In improved the thermoelectricperformance; thus, the dimensionless figure of merit obtained at 623 K for Cu3Sb0.86Ge0.08In0.06Se4, was 0.47.

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