Synergistically Optimized Electron and Phonon Transport of Polycrystalline BiCuSeO via Pb and Yb Co-Doping

Polycrystalline BiCuSeO is considered as a promising thermoelectric material due to its intrinsically low thermal conductivity and moderate Seebeck coefficient. However, its low electrical conductivity and coupled electron-phonon transport properties restrict the further improvement of the thermoelectric performance. In this work, Pb and Yb dopants are incorporated into BiCuSeO to substitute for Bi sites via ball milling and high-pressure and high-temperature sintering, leading to a synergistic optimization of the electron and phonon transport and improved thermoelectric performance. The carrier concentration exhibits an enhancement with increasing Pb&Yb co-doping contents. Meanwhile, the decreased carrier mobility is suppressed appropriately by coordinating with the interplay of Pb and Yb dopants on the electronic structure. Besides, Pb&Yb co-doping combined with high-pressure and high-temperature sintering introduces abundant grain boundaries, dislocations, and point defects to effectively decrease the lattice thermal conductivity by scattering phonons in a broad frequency range. Coupled with the synergistic optimization of the electrical and thermal properties, a maximum zT of 1.2 is achieved in Bi_0.88Pb_0.06Yb_0.06CuSeO at 850 K, which significantly outperforms the majority of oxygen-containing thermoelectric materials. Our study suggests that dual doping of bivalent ions and rare-earth elements at Bi sites is an effective strategy for improving the thermoelectric performance of BiCuSeO.