Effect of ball milling time on the thermoelectric properties of p-type (Bi,Sb)2Te3

• P-type (Bi,Sb)2Te3 compounds were fabricated with the ball-milled powders.
• Finer grain sizes were confirmed in the samples after long milling time.
• Thermoelectric properties were largely dependent on milling time.
• The carrier concentration was changed with the milling time.
• ZT = 1.14 at 323 K was achieved for the samples with the optimized milling time.

P-type (Bi,Sb)2Te3 compounds were fabricated with high energy ball-milled powder and their thermoelectric properties were investigated as a function of the ball milling time. The fine grain sizes were confirmed with the X-ray analysis and the microscopy images in the samples fabricated with powders from long ball milling time. The values of the lattice thermal conductivity of the samples at high temperature show smaller values for long milling time (>24 h) than those for short time, resulted from the finer grain sizes of the samples. As well as the microstructural change, the Seebeck coefficient and the electrical resistivity of the compounds were significantly altered with the ball milling time. The carrier concentration was dramatically increased in the samples after 24 h milling, which was attributed to the formation of the antisite defects introduced by the accumulated thermal energy. The formation of antisite defects may be also promoted by the unintentional Fe doping from jars and balls. The highest value of ZT = 1.14 was achieved at 323 K for the samples with 10 h. The temperature where the value of ZT was maximized and the values of ZT was varied with the ball milling time, which implies that the ball milling time should be carefully optimized for the suitable application of this compounds.