Fast, sensitive, and precise detection of nitric oxide (NO) is critical to many applications in environmental monitoring and early disease diagnosis via respiratory testing. An effective detection system requires a sensor to detect NO gas at the parts per billion (ppb) level, and this system should possess a high degree of anti-interference selectivity. To achieve these targets, a series of gas sensor thin films based on intrinsic WO3, one-additive-doped WO3 (prepared by doping In2O3 or Nb2O5), and two-additive-doped WO3 (synthesized by doping with In2O3 and Nb2O5) oxides were successfully grown. By analyzing the properties of sensitivity, selectivity, responsiveness, and recovery time of the gas sensors, we found that WO3-1wt%In2O3-1wt%Nb2O5 has overwhelming advantages over intrinsic WO3, WO3-In2O3, and WO3-Nb2O5. A sensing response value of 2.4 was observed for NO concentrations as low as 20 ppb from the WO3-1wt%In2O3-1wt%Nb2O5 sensor. With 100 ppb NO gas, the WO3-1wt%In2O3-1wt%Nb2O5 sensor achieved a high response of 56.1 at 70 °C, which is a state-of-the-art performance for NO detection at low working temperature settings. WO3-1wt%In2O3-1wt%Nb2O5 also yields significantly improved selectivity and stability over intrinsic WO3, WO3-In2O3, and WO3-Nb2O5. Studies on the sensing mechanism show that the grain size, rather than the n-n heterostructure effect, plays a dominant role in the observed results. By decreasing the grain size so that it is close to the thickness of the space-charge layer, the sensing response is enhanced. Although room remains to further improve the sensing properties, the performance of WO3-1wt%In2O3-1wt%Nb2O5 is sufficient for implementation in low-content NO detection devices.
Keywords: NO gas sensor; codoping; high selectivity; limit of detection (LOD); ppb-level response; pulsed laser deposition (PLD).