Enhanced Thermoelectric Properties of Cu2SnSe3 by (Ag,In)‐Co‐Doping

Dense bulk samples of (Ag,In)‐co‐doped Cu₂SnSe₃ have been prepared by a fast and one‐step method of combustion synthesis, and their thermoelectric properties have been investigated from 323 to 823 K. The experimental results show that Ag‐doping at Cu site remarkably enhances the Seebeck coefficient, reduces both electrical and thermal conductivities, and finally increases the figure of merit (ZT) value. The ZT of the Cu_1.85Ag_0.15SnSe₃ sample reaches 0.80 at 773 K, which is improved by about 70% compared with the unadulterated sample (ZT = 0.46 at 773 K). First principle calculation indicates that Ag‐doping changes the electronic structure of Cu₂SnSe₃ and results in larger effective mass of carriers, thus enhancing the Seebeck coefficient and reducing the electrical conductivity. The low electrical conductivity caused by Ag‐doping can be repaired by accompanying In‐doping at Sn site, and by (Ag,In)‐co‐doping the thermoelectric properties are further promoted. The (Ag,In)‐co‐doped sample of Cu_1.85Ag_0.15Sn_0.9In_0.1Se₃ shows the maximum ZT of 1.42 at 823 K, which is likely the best result for Cu₂SnSe₃‐based materials up to now. This work indicates that co‐doping may provide an effective solution to optimize the conflicting material properties for increasing ZT.