Intrinsic and metal-doped gallium oxide based high-temperature oxygen sensors for combustion processes

Currently, there is enormous interest in research, development and optimization of the combustion processes for energy harvesting. Recent statistical and economic analyses estimated that by improving the coal-based firing/combustion processes in the power plants, savings up to ~$450-500 million yearly can be achieved. Advanced sensors and controls capable of withstanding extreme environments such as high temperatures, highly corrosive atmospheres, and high pressures are critical to such efficiency enhancement and cost savings. For instance, optimization of the combustion processes in power generation systems can be achieved by sensing, monitoring and control of oxygen, which is a measure of the completeness of the process and can lead to enhanced efficiency and reduced greenhouse gas emissions. However, despite the fact that there exists a very high demand for advanced sensors, the existing technologies suffer from poor ‘response and recovery times’ and ‘long-term stability.’ Motivated by the aforementioned technological challenges, the present work was focused on high-temperature (≥700 °C) oxygen sensors for application in power generation systems. The objective of the present work is to investigate nanostructured gallium oxide (2O3) based sensors for oxygen sensing, where we propose to conduct in-depth exploration of the role of refractory metal (tungsten, W, in this case) doping into 2O 3 to enhance the sensitivity, selectivity, stability (“3S” criteria) and reliability of such sensors while keeping cost economical. Tungsten (W) doped gallium oxide (2O3) thin films were deposited via rf-magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying the sputtering power applied to the W-target in order to achieve variable W content into 2O3 films while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-grown and post-annealed W-doped 2O3 films were evaluated as a function of W-content. The structural analyses indicate the formation of monoclinic β-phase 2O3 in as-grown W-doped 2O3 films for all W-content. Thermally induced secondary phase (W-oxide) formation was observed after the annealing process. Chemical analysis demonstrates the increasing W atomic percentage in the films with increasing sputtering power, whereas the main metallic ionic species for the films are W6+ and Ga3+. Evidence of W interdiffusion due to the annealing process is presented, and the mechanism of diffusion is discussed. Surface morphology of the films is also discussed, and the transition to mesoporous surface is observed after annealing. Finally, the oxygen sensor performance evaluation demonstrated that the W-incorporated 2O3 exhibits improved response time compared to intrinsic 2O3 based oxygen sensors