On the high-temperature oxidation of ZnSb for thermoelectric applications

Thermoelectric ZnSb has a native surface oxide layer of Sb2O5 +ZnO, while HT oxidation in air resulted in selective oxidation to ZnO, with no detectable Sb by STEM-EDS. The ZnO consisted of an inner nano-granular and a more columnar outer layer. Thermogravimetry showed parabolic oxidation kinetics at 200–325 °C with an activation energy of 117 kJ/mol, comparing well with literature for oxidation of Zn. Two-stage 16O2 +18O2 oxidation followed by SIMS suggests growth by mixed Zn and O diffusion through a protective ZnO layer that still cannot prevent considerable high temperature oxidation in air, with formation of insulating electrical contacts, unless metallised.