Bi2Te3 single crystals with high room-temperature thermoelectric performance enhanced by manipulating point defects based on first-principles calculation

Intrinsic Bi₂Te₃ is a representative thermoelectric (TE) material with high performance at low temperature, which enables applications for electronic cooling. However, antisite defects easily form in p-type Bi₂Te₃, resulting in the difficulty of further property enhancement. In this work, the formation energy of native point defects in Bi₂Te₃ supercells and the electronic structure of Bi₂Te₃ primitive unit cell were calculated using first-principles. The antisite defect Bi_Te₁ has a lower formation energy (0.68 eV) under the Te-lack condition for p-type Bi₂Te₃. The effects of point defects on TE properties were investigated via a series of p-type Bi₂Te_3−x (x = 0, 0.02, 0.04, 0.06, 0.08) single crystals prepared by the temperature gradient growth method (TGGM). Apart from the increased power factor (PF_∥) which originates from the increased carrier concentration (n_∥) and m*, the thermal conductivity (κ_∥) was also cut down by the increased point defects. Benefitting from the high PF_∥ of 4.09 mW m⁻¹ K⁻² and the low κ_∥ of 1.77 W m⁻¹ K⁻¹, the highest ZT_∥ of 0.70 was obtained for x = 0.06 composition at 300 K, which is 30% higher than that (0.54) of the intrinsic Bi₂Te₃.

This study prepared Bi₂Te₃ single crystals and investigated the thermoelectric properties of Bi₂Te₃ based on the electronic structure and formation energy of point defects which are calculated by density functional theory.