Low electrical resistivity polycrystalline TiO2-based transparent conductive thin films by DC magnetron sputter deposition

Transparent conductive oxides (TCO), mainly In2O3:Sn (ITO), ZnO:Al (AZO) and SnO2:F (FTO) are widely used as transparent electrodes in flat panel displays, thin film solar cells and solid state lighting. The markets for the applications requiring large area electrodes are continuously growing recent years which drives the need for a cost-efficient replacement of conventional TCOs. In addition to a low cost, TiO2 offers unique combination of high refractive index, stability against humidity, the high chemical stability and the non-toxicity. The Nb or Ta doped TiO2 films epitaxially grown on crystalline substrates show electrical and optical properties which are comparable to those of conventional TCOs. However, using expensive crystalline substrates drastically limits applications. It is still a challenge to achieve low electrical resistivity polycrystalline TiO2 films as required for the most applications. Furthermore, it is not possible to get low resistivity in polycrystalline films by direct growth at elevated substrate temperature.
Only a two-step approach containing the deposition of amorphous films followed by annealing in vacuum or hydrogen delivers films with resistivity values in the range of 1·10-3 cm. Even in that case, it is known that electrical, optical and structural properties evolution during crystallization, and crystallization itself, is strongly affected by the Ti/O ratio in the as-deposited films. Achieving required Ti/O ratio remains the main challenge. In order to address this problem, we studied the films formed on glass substrates without heating by DC magnetron sputtering of reduced TiO2-x:Ta ceramic targets followed by vacuum annealing. We achieved oxygen fine-tuning using a MS process in conjunction with a plasma feedback system. The optimum total pressure in combination with O2 fine tuning yielded the films with the best free electron mobility of 8 cm²/Vs. Our approach delivered films with an electrical resistivity in the range of 10-3 W cm, optical transmittance above 80% for 400nm thick films and electrical activation of Ta dopants up to 70% which is substantially higher than that of Al in ZnO. The temperature dependent hall effect measurements show a different behavior of the resistivity vs. temperature with varying film stoichiometry.