Thermoelectric Performance and First Principles Calculations of the Type-VIII Clathrates Ba8Ga16–xAgxSn30
摘要
Single crystals of the n-type type-VIII clathrate Ba8Ga16–xAgxSn30 (x = 0, 0.5, 1) were synthesized using the Sn-flux method. Elemental analysis reveals an extremely low actual Ag incorporation (xreal ≈ 0.034–0.037) despite much higher nominal compositions. From a theoretical standpoint, the structural and electronic properties of the Ag-substituted type-VIII clathrate Ba8Ga16–xAgxSn30 were systematically investigated using first-principles calculations. All samples exhibited negative Seebeck coefficients across the measured temperature range, confirming their n-type conduction. However, the results derived from theoretical calculations indicated that all samples displayed p-type conduction behavior. The interesting discrepancy between the experimental and computational results is attributed to variations in the ratio of framework atoms. Detailed analysis confirmed that these clathrates are indirect bandgap semiconductors, with the bandgap widening as the Ag doping concentration increases. Experimentally, the magnitude of the Seebeck coefficient for the x = 1 sample reached approximately 330 μV K–1 at 600 K. Furthermore, the temperature-dependent transport properties of these clathrates are consistent with the typical behavior of heavily doped semiconductors. Consequently, the x = 1 sample achieved a maximum power factor of 1.49 × 10–3 W m–1 K–2 at approximately 540 K. Among all synthesized Ba8Ga16–xAgxSn30 compounds, the x = 1 sample exhibited the highest thermoelectric performance across the measured temperature range, reaching an estimated maximum figure of merit of 1.2 at 600 K.