Towards p-Type Conductivity in SnO2Nanocrystals through Li Doping and Its Applications in Porous Diodes for Room Temperature Chlorine Gas Detection

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This work examined electrical transport properties and Li doping in SnO2synthesized by the sol–gel method. Solid-state 7Li-NMR line shapes revealed that Li ions occupy two distinct sites with differing dynamic mobilities. The chemical exchange rate between the two sites is, however, too slow for detection on the NMR timescale. Compressed nanoparticulate films of this doped semiconductor exhibited a positive Seebeck coefficient implying a p-type conductivity. A variable-temperature direct current conductivity, over a 25–350 °C temperature range, followed an Efros–Shklovskii variable range hopping (ES-VRH) conduction mechanism (ln(ρ) versus T−1/2) at temperatures below 100 °C with a crossover to 2D Mott variable range hopping (M-VRH) (ln(ρ) versus T−1/3) conduction at temperatures above 250 °C. In a transition region between these two limiting behaviors, direct current resistivity exhibited an anomalous temperature-independent plateau. We suggest that its origin may lie in a carrier inversion phenomenon wherein the majority carriers switch from holes to electrons due to Li ion expulsion from the crystalline core and creation of oxygen vacancies generated by loss of oxygen at elevated temperatures. Using a compression technique, porous diodes consisting of n-type (antimony doped SnO2) and the p-type (lithium-doped) nano-particulate films were prepared. Typical current-voltage curves of such devices resembled the behavior of a typical diode but for one key difference; owing to the porosity of the film, areas near the p-n interface and the p- and n-regions are accessible to gaseous analytes. This access is not possible in conventional diodes fabricated through contemporary planar technology. The gas sensing properties of the diodes were investigated by using Cl2, Br2, HCl, NO, NO2, CHCl3, NH3 and H2. Of all the gases tested, the sensor had very good sensitivity to Cl2 and had a response of 80 at 400 ppb of Cl2. The response time of the sensor was ~30 s at room temperature but the recovery time was temperature dependent. At room temperature the recovery time was 80s after 400 ppb chlorine exposure. The sensors were also found to recover quickly (~ 30 s) when the junctions were biased. Reverse biasing the diode provides a controllable band-bending at a p-n junction that could influence the electron-transfer rates from the adsorbates which create intra-band localized states. As a result reverse biasing can provide a means of desorbing the analyzed species. This approach eliminates the requirement to remove adsorbates by elevating the sensor temperature and hence improves on the energy efficiency of these types of sensors.

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