Influence of vacancies on the electrical properties of the ZnCr2−xNixSe4 spinels

The effect of vacancies on the electronic transport in the ZnCr_2−xNi_xSe₄ paramagnetic single crystals is considered. For this purpose, the structure refinements, the high temperature electrical conductivity and the thermoelectric power measurements as well as the calculations of the vacancy model parameters were used. The electrical measurements have been done in the temperature range from 290 to 520 K for single crystals with x=0.001, 0.05, and 0.065. The above investigations provide evidence for polaron conduction in defective spinel materials. In particular: (1) at high temperatures a linear dependence between thermopower S and the electrical resistivity (ln ρ), a characteristic of small polarons, was observed, (2) an origin of small polarons in this case could be associated with a crystalline distortion, which is characterized by larger values of the anion parameter than u=0.375, which describes an ideal spinel structure, and (3) a large defectiveness, which is identified by the large value of the vacancy parameter of about β=11.5%. These effects are explained in terms of a polaron mechanism of the electrical conductivity including structural defects.