Thermoelectric properties of nanostructured Al-substituted ZnO thin films

ZnO:Al nano-polycrystalline thin films were deposited by radio-frequency magnetron sputtering on glass substrates. The analysis of the morphology reveals well-connected whiskers with a preferred c-axis orientation perpendicular to the substrate and a dense columnar grain structure. The as-deposited films exhibited a low electrical resistivity of 1 × 10−3 Ω cm. Annealing in air produces an increase of the resistivity by more than three orders of magnitude and an increase in the absolute value of the Seebeck coefficient proportional to the resistivity. Annealing of the as-deposited sample in reducing Ar/H2 atmosphere leads to a decrease in both the resistivity and the absolute value of the Seebeck coefficient. The change in the electrical transport properties is caused by the absorption and desorption of oxygen. Both resistivity and Seebeck coefficient recover to their initial values during annealing of the air-treated sample in reducing Ar/H2 atmosphere, indicating a reversible process. The analysis by transmission electron microscopy after annealing reveals a stable columnar grain structure with an increase of the grain size. The increase in grain size is larger when the sample is annealed in reducing rather than in oxidising atmosphere. In summary, the reducing Ar/H2 atmosphere was found to be advantageous for the thermoelectric properties resulting in a maximum power factor of 0.3 mW/K2m at 800 K. - Highlights: ► Thermoelectric ZnO:Al films were reproducibly deposited by magnetron sputtering. ► Electron microscopy studies reveal a dense structure and columnar growth. ► Thermoelectric properties of the films depend on the cycling atmosphere. ► We report reversible thermochemical behaviour during heating cooling cycles. ► A relatively large power factor was measured at elevated temperatures.