Stepwise Vacancy Manipulation for Optimized Carrier Concentration and Blocked Phonon Transport Realizing Record High Figure of Merit <i>zT</i> in CuInTe₂

Abstract Great enhancement in the thermoelectric performance of CuInTe 2 is achieved through stepwise regulation of Cu vacancies. Lowering Cu content can effective introduce large number of Cu vacancies, which is substantiated by positron annihilation measurements. The carrier concentration is thereby successfully tuned from 5.5× 10 18 cm −3 to 3.2× 10 19 cm −3 . The Cu vacancies strongly suppress the lattice thermal conductivity due to both enhanced phonon scattering and lowered phonon velocity. As a consequence, a high zT value exceeding 1.2 at 773 K is achieved in Cu 0.95 InTe 2 with optimal carrier concentration of 1.65× 10 19 cm −3 . The highly Cu deficient Cu 0.90 InTe 2 sample is further doped with Bi, which can fill the excessive Cu vacancies. The Bi dopants introduce mass and strain fluctuation, and also cause modulation of lattice structure to form ordered superstructures, which all enhance phonon scattering. In addition, Bi doping results in severe lattice softening, which significantly reduces phonon velocity. As a result, an extremely low lattice thermal conductivity of 1.19 W m −1 K −1 is reached at 300 K. Eventually, a record high zT value of 1.8 at 773 K is achieved in the Cu 0.90 Bi 0.06 InTe 2 sample, which is almost three times that of the pristine CuInTe 2 , reaching the leading level for CuInTe 2 ‐based materials.