Oxygen Adsorption and Desorption Kinetics in CuO Nanowire Bundle Networks: Implications for MOx-Based Gas Sensors

Abstract

Copper oxide (CuO) nanostructures have demonstrated a good chemiresistive response for the sensing of various gases. The precise sensing mechanisms of this material and, in particular, the kinetics of the response to gases and the sensor recovery remain much less investigated. For metal oxide (MOx) chemiresistive gas sensors, oxygen adsorption and desorption reactions on a material surface play a major role in the sensor kinetics, as most other gases react with oxygen on the sensor surface in order to provide the sensing signal, and nanoscale materials are known to achieve faster response. Here we investigate the oxygen adsorption and desorption kinetics on CuO nanowire bundle (NWB) networks by analyzing the electrical response and recovery curves of sensing devices exposed to oxygen. The observation of multiple time constants for the response and recovery curves led us to discuss the various potential mechanisms related to surface reaction kinetics and diffusion of oxygen species. By comparing the reaction rate constants and diffusion constants extracted from the obtained time constants, we conclude that the diffusion of oxygen defects into the material might be the main reason for the observed large time constants. Surprisingly, we observe that the sensor devices based on as-deposited materials show 4–16 times faster response and recovery as compared to devices after being annealed, depending on the temperature. By comparing this result with detailed characterization using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, we discuss the role of the junctions between nanostructures in the network and of the hydroxylated CuO surface to explain this result. Our investigation on the kinetics of adsorption and desorption of oxygen of CuO NWB provides a direct understanding of the general response of the sensor and will be useful in order to further understand and optimize these materials for the sensing of various gases.