Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al2O3 on Corning glass at substrate temperature of 150 °C with Ar/CF4/H2 gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9–4 × 10−4 Ω cm and very low absorption coefficient below 900 cm−1 when averaged in 400–800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10−4 Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω−1, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.