Distinguishing Bulk Conduction from Band Bending Transduction Mechanisms in Chemiresistive Metal Oxide Gas Sensors

Chemiresistive metal oxide gas sensors based on materials including SnO 2, ZnO, TiO 2, and WO 3 have been investigated extensively for a wide range of applications. The band bending model, based on the surface chemistry of highly reactive ionosorbed species (O 2 – or O – ) and the semiconducting material properties of SnO 2, TiO 2, and ZnO, adequately predicts the dependence of steady state response on target gas pressure and temperature for these materials. However, the assumptions associated with the band bending model are not valid for sensors based on reducible oxides such as WO 3, MoO 3, and V 2 O 5, in which lattice oxygen reacts with adsorbed target gases creating oxygen vacancies which diffuse rapidly into the bulk and modulate the conductivity. Here, we develop a model that includes surface reactions and vacancy diffusion for the bulk conduction mechanism and describe characteristics of the sensor behavior that allow bulk conduction to be distinguished from the band bending transduction mechanism. We illustrate the predictions of the model regarding how the change in conductivity, Δσ, and response time, τ, depend on target gas pressure, temperature, and film thickness using well-characterized WO 3 sensors, including epitaxially oriented polycrystalline thin films and nanorod structured glancing angle deposition (GLAD) films. The physical/chemical parameters of the model are determined in independent measurements. Expressions for the limiting cases in which τ is determined either by surface reactions or by bulk diffusion provide design criteria to predict the theoretical performance limits of sensors which operate via this transduction mechanism.