RESUMEN
Bismuth telluride-based alloys are the best performing thermoelectric materials near room temperature. Grain size refinement and nanostructuring are the core stratagems for improving thermoelectric and mechanical properties. However, the donor-like effect induced by grain size refinement strongly restricts the thermoelectric properties especially in the vicinity of room temperature. In this study, the formation mechanism for the donor-like effect in Bi2Te3-based compounds was revealed by synthesizing five batches of polycrystalline samples. We demonstrate that the donor-like effect in Bi2Te3-based compounds is strongly related to the vacancy defects (VBiâ´ and VTe···) induced by the fracturing process and oxygen in air for the first time. The oxygen-induced donor-like effect dramatically increases the carrier concentration from 2.5 × 1019 cm-3 for the zone melting ingot and bulks sintered with powders ground under an inert atmosphere to 7.5 × 1019 cm-3, which is largely beyond the optimum carrier concentration and seriously deteriorates the thermoelectric performance. Moreover, it is found that both avoiding exposure to air and eliminating the thermal vacancy defects (VBiâ´ and VTe···) via heat treatment before exposure to air can effectively remove the donor-like effect, producing almost the same carrier concentration and Seebeck coefficient as those of the zone melting ingot for these samples. Therefore, a defect equation of oxygen-induced donor-like effect was proposed and was further explicitly corroborated by positron annihilation measurement. With the removal of donor-like effect and improved texturing via multiple hot deformation (HD) processes, a maximum power factor of 3.5 mW m-1 K-2 and a reproducible maximum ZT value of 1.01 near room temperature are achieved. This newly proposed defect equation of the oxygen-induced donor-like effect will provide a guideline for developing higher-performance V2VI3 polycrystalline materials for near-room-temperature applications.