The creation of crystal phase heterostructures of transition metal chalcogenides, e.g., the 1T/2H heterostructures, has led to the formation of metal/semiconductor junctions with low potential barriers. Very differently, post-transition metal chalcogenides are semiconductors regardless of their phases. Herein, we report, based on experimental and simulation results, that alloying between 1T-SnS2 and 1T-WS2 induces a charge redistribution in Sn and W to realize metallic Sn0.5W0.5S2 nanosheets. These nanosheets are epitaxially deposited on surfaces of semiconducting SnS2 nanoplates to form vertical heterostructures. The ohmic-like contact formed at the Sn0.5W0.5S2/SnS2 heterointerface affords rapid transport of charge carriers, and allows for the fabrication of fast photodetectors. Such facile charge transfer, combined with a high surface affinity for acetone molecules, further enables their use as highly selective 100 ppb level acetone sensors. Our work suggests that combining compositional and structural control in solution-phase epitaxy holds promises for solution-processible thin-film optoelectronics and sensors.

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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 = R g/R a) 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.

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.

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