The improvement of thermoelectric property of bulk ZnO via ZnS addition: Influence of intrinsic defects

As in any semiconducting solids, intrinsic defects can affect the properties of ZnO, such as the electrical and thermal conductivities. Defect engineering is usually focused on optimizing the materials’ synthesis or annealing parameters, i.e., temperature, atmosphere, etc. Here we report an approach to change the intrinsic defects of ZnO by adding a small amount of ZnS. During the sintering process, ZnS was decomposed. Apart from the formation of SO₂, the decomposed S and Zn can also be simultaneously doped onto O and Zn sites to change the intrinsic defects in ZnO. For instance, some of the S was converted to SO₂ and led to the formation of V_o (oxygen vacancy); meanwhile, Zn may move to the V_Zn (Zn vacancy) site and decrease the concentration of Zn vacancy. Due to the changes in these native defects, the carrier concentration increased and the thermal conductivity decreased when the content of ZnS was increased to x = 0.01. This sample had an optimal zT value, which was twice that of undoped ZnO. However, with further increase in ZnS, the carrier concentration was reduced. These results suggest a method to tune the intrinsic defects of ZnO via doping technology and bring potential opportunities to improve the thermoelectric performance of this oxide.