Temperature-Dependent Abnormal and Tunable p-n Response of Tungsten Oxide--Tin Oxide Based Gas Sensors.

We observed the sensing response of temperature-dependent abnormal p-n transitions in WO3-SnO2 hybrid hollow sphere based gas sensors for the first time. The sensors presented a normal n-type response to ethanol at elevated temperatures but abnormal p-type responses in a wide range of operation temperatures (room temperature to about 95 °C). By measuring various reducing gases and applying complex impedance plotting techniques, we demonstrated the abnormal p-type sensing behavior to be a pseudo-response resulting from the reaction between target gas and adsorbed water on the material surface. The temperature-controlled n-p switch is ascribed to the competition of intrinsic and extrinsic sensing behaviors, which resulted from the reaction of target gas with adsorbed oxygen ions and protons from adsorbed water, respectively. The former can modulate the intrinsic conductivity of the sensor by changing the electron concentration of the sensing materials, while the latter can regulate the conduction of the water layer, which contributes to the total conductivity as an external part. The hollow and hybrid nanostructures facilitated the observation of extrinsic sensing behaviors due to its large-area active sites and abundant oxygen vacancies, which could enhance the adsorption of water. This work might give new insight into gas sensing mechanisms and opens up a promising way to develop practical temperature and humidity controllable gas sensors with little power consumption based on the extrinsic properties.