Adjustment of oxygen vacancy states in ZnO and its application in ppb-level NO₂ gas sensor

Oxygen vacancy (V_O) is long believed as a key factor influencing the gas sensing properties. However, the concentration of V_O is generally focused while the V_O state is neglected, which masks the inherent mechanism of gas sensor. Using a post annealing process, the influence of V_O states on the response of ZnO nanofilm to NO₂ gas is investigated in this study. The systematical analysis of the results obtained by different methods indicates a transformation of V_O from the neutral to the doubly ionized state during post annealing treatment. The results also imply that the gas sensing properties is not directly correlated with the V_O concentration. And due to the competitive adsorption of ambient O₂, the neutral V_O is majorly occupied by the adsorbed O₂ while the V_O in doubly ionized state can promote the adsorption of NO₂. Consequently, the transition of V_O from the neutral to the doubly ionized state can lead to a dramatic increase of the response to NO₂, from 733 to 3.34 × 10⁴ for 100 ppm NO₂. Guided by this mechanism, NO₂ gas sensing in ppb-level is also achieved: the response reaches 165% to 25 ppb (0.025 ppm) NO₂ with a good repeatability.