Effects of Sb compensation on microstructure, thermoelectric properties and point defect of CoSb₃ compound

Volatilization of Sb during the fabrication of CoSb₃ by mechanical alloying and then spark plasma sintering has been successfully compensated by adding excess Sb. The average grain size increases apparently with excess Sb content, abnormally grown by about 100 times as the excess Sb is up to 4 at.%. A liquid-phase-related mechanism is used to explain the abnormal growth. The uncompensated sample shows a negative Seebeck coefficient near room temperature, while the sample compensated with 6 at.% excess Sb shows an intrinsic positive Seebeck coefficient and an enhanced ZT value, which has a maximum of about 0.1 at 350 °C, which is two times higher than the uncompensated one. The transition of electrical conductivity from n- to p-type relative to the Sb compensation is discussed in relation to the point defect. A defect equation is given to show the nature of electron generation due to Sb deficiency. The Sb-vacancy not only provides extrinsic carrier but also generates a significant impact on the band gap and hence on the Seebeck coefficient.