Adsorbed Oxygen Ions and Oxygen Vacancies: Their Concentration and Distribution in Metal Oxide Chemical Sensors and Influencing Role in Sensitivity and Sensing Mechanisms

Oxidation reactions on semiconducting metal oxide (SMOs) surfaces have been extensively worked on in catalysis, fuel cells, and sensors. SMOs engage powerfully in energy-related applications such as batteries, supercapacitors, solid oxide fuel cells (SOFCs), and sensors. A deep understanding of SMO surface and oxygen interactions and defect engineering has become significant because all of the above-mentioned applications are based on the adsorption/absorption and consumption/transportation of adsorbed (physisorbed-chemisorbed) oxygen. More understanding of adsorbed oxygen and oxygen vacancies (VO•,VO••) is needed, as the former is the vital requirement for sensing chemical reactions, while the latter facilitates the replenishment of adsorbed oxygen ions on the surface. We determined the relation between sensor response (sensitivity) and the amounts of adsorbed oxygen ions (O2(ads)−, O(ads), −O2(ads)2−, O(ads)2−), water/hydroxide groups (H2O/OH−), oxygen vacancies (VO•, VO••), and ordinary lattice oxygen ions (Olattice2−) as a function of temperature. During hydrogen (H2) testing, the different oxidation states (W6+, W5+, and W4+) of WO3 were quantified and correlated with oxygen vacancy formation (VO•, VO••). We used a combined application of XPS, UPS, XPEEM-LEEM, and chemical, electrical, and sensory analysis for H2 sensing. The sensor response was extraordinarily high: 424 against H2 at a temperature of 250 °C was recorded and explained on the basis of defect engineering, including oxygen vacancies and chemisorbed oxygen ions and surface stoichiometry of WO3. We established a correlation between the H2 sensing mechanism of WO3, sensor signal magnitude, the amount of adsorbed oxygen ions, and sensor testing temperature. This paper also provides a review of the detection, quantification, and identification of different adsorbed oxygen species. The different surface and bulk-sensitive characterization techniques relevant to analyzing the SMOs-based sensor are tabulated, providing the sensor designer with the chemical, physical, and electronic information extracted from each technique.