Surface-Catalyzed Zinc Oxide Nanorods and Interconnected Tetrapods as Efficient Methane Gas Sensing Platforms

Abstract

Nanostructured metal oxide semiconductors have proven to be promising for the gas sensing domain. However, there are challenges associated with the fabrication of high-performance, low-to-room-temperature operation sensors for methane and other gases, including hydrogen sulfide, carbon dioxide, and ammonia. The functional properties of these semiconducting oxides can be improved by altering the morphology, crystal size, shape, and topology. Zinc oxide (ZnO) is an attractive option for gas sensing, but the need for elevated operating temperatures has limited its practical use as a commercial gas sensor. In this work, we prepared ZnO nanorod (ZnO-NR) arrays and interconnected tetrapod ZnO (T-ZnO) network sensing platforms as chemiresistive methane sensors on silicon substrates with platinum interdigitated electrodes and systematically characterized their methane sensing response in addition to their structural and physical properties. We also conducted surface modification by photochemical-catalyzed palladium, Pd, and Pd-Ag alloy nanoparticles and compared the uniformly distributed Pd decoration versus arrayed dots. The sensing performance was assessed in terms of target gas response magnitude (RM) and response percentage (R) recorded by changes in electrical resistance upon exposure to varying methane concentration (100–10,000 ppm) under thermal (operating temperatures = 175, 200, 230 °C) and optical (UV A, 365 nm illumination) excitations alongside response/recovery times, and limit of detection quantification. Thin film sensing platforms based on T-ZnO exhibited the highest response at 200 °C (RM = 2.98; R = 66.4%) compared to ZnO-NR thin films at 230 °C (RM = 1.34; R = 25.5%), attributed to the interconnected network and effective bandgap and barrier height reduction of the T-ZnO. The Pd-Ag-catalyzed and Pd dot-catalyzed T-ZnO films had the fastest response and recovery rates at 200 °C and room temperature under UV excitation, due to the localized Pd nanoparticles dots resulting in nano Schottky barrier formation, as opposed to the films coated with uniformly distributed Pd nanoparticles. The experimental findings present morphological differences, identify various mechanistic aspects, and discern chemical pathways for methane sensing.