Complex electronic structure and compositing effect in high performance thermoelectric BiCuSeO.

BiCuSeO oxyselenides are promising thermoelectric materials, yet further thermoelectric figure of merit ZT improvement is largely limited by the inferior electrical transport properties. The established literature on these materials shows only one power factor maximum upon carrier concentration optimization, which is typical for most thermoelectric semiconductors. Surprisingly, we found three power factor maxima when doping Bi with Pb. Based on our first-principles calculations, numerical modeling, and experimental investigation, we attribute the three maxima to the Fermi energy optimization, band convergence, and compositing effect due to in situ formed PbSe precipitates. Consequently, three ZT peaks of 0.9, 1.1, and 1.3 at 873 K are achieved for 4, 10, and 14 at.% Pb-doped samples, respectively, revealing the significance of complex electronic structure and multiple roles of Pb in BiCuSeO. The results establish an accurate band structure characterization for BiCuSeO and identify the role of band convergence and nanoprecipitation as the driving mechanism for high ZT.