Observation of Switchable Dual-Conductive Channels and Related Nitric Oxide Gas-Sensing Properties in the N-rGO/ZnO Heterogeneous Structure

Gas sensors based on hybrid materials of graphene oxide/metal oxide semiconductors are an effective way to improve sensor performance. In this paper, we demonstrate a high-performance nitric oxide (NO) gas sensor based on nitrogen-doped reduced graphene oxide/ZnO nanocrystals (N-rGO/ZnO) operating at a low work temperature. ZnO nanocrystals, with an average size of approximately 5 nm, can be uniformly and compactly anchored on the surface of N-rGO using a facile two-step hydrothermal synthesis with an appropriate amount of ammonia as the nitrogen source. The sensor based on the N-rGO/ZnO composite with 0.3 mL of ammonia (N-rGO/ZnO-0.3), in comparison with N-rGO/ZnO with different amounts of ammonia, N-rGO, and rGO/ZnO, exhibited a significantly higher sensitivity (S = Rg/Ra) at the parts per billion (ppb) level for NO gas at 90 °C. The maximum sensitivity at 800 ppb NO was approximately 22, with much faster response and recovery times. In addition, the N-rGO/ZnO-0.3 sensor revealed great stability, a low detection limit of 100 ppb, and an excellent selectivity toward NO versus other gases (NO2, H2, CO, NH3, and CH4), especially at the ppb level. More interestingly, when exposed to oxidizing and reducing gases, unlike conventional semiconductor sensitive materials with resistances that normally change in the opposite direction, only the increase in the resistance is surprisingly and incomprehensibly observed for the N-rGO/ZnO-0.3 sensor. The peculiar sensing behaviors cannot be explained by the conventional theory of the adsorption process, redox reactions on the surfaces, and the well-defined p–n junction between N-rGO and ZnO, originating from the chemical bonding of Zn–C. We propose here for the first time that switchable contribution from dual-conduction paths including the corresponding ZnO channel with the p–n junction and the corresponding N-rGO channel to the sensitivity may exist in the interaction between gases and N-rGO/ZnO-0.3 material. When an oxidizing gas (such as NO) is exposed to the N-rGO/ZnO-0.3 sensor, the contribution from the conductive channel of ZnO nanoparticles and the p–n junction to the sensitivity is dominant. On the contrary, as for a reducing gas (such as H2), the contribution alters to the N-rGO channel as the dominating mode for sensitivity. For gas-sensing behavior of the NGZ-0.1 and NGZ-0.5 sensors, there is only one conduction path from the N-rGO channel for the sensitivity. The model of switchable dual-conduction paths has addressed the mysterious response observed for different gases, which may be utilized to enlighten the understanding of other application problems in nanoscale hybrid materials with a heterogeneous structure.