Sacrificial Doping as an Approach to Controlling the Energy Properties of Adsorption Sites in Gas-Sensitive ZnO Nanowires

Currently, devices for environmental gas analyses are required in many areas of application. Among such devices, semiconductor-resistive gas sensors differ advantageously. However, their characteristics need further improvement. The development of methods for controlling the surface properties of nanostructured metal oxides for their use as gas sensors is of great interest. In this paper, a method involving the sacrificial doping of ZnO nanowires to control the content of their surface defects (oxygen vacancies) was proposed. Zinc oxide nanowires were synthesized using the hydrothermal method with sodium iodide or bromide as an additional precursor. The surface composition was studied using X-ray photoelectron spectroscopy. The sensor properties of the isopropyl alcohol vapors at 150 °C were studied. It was shown that a higher concentration of oxygen vacancies/hydroxyl groups was observed on the surfaces of the samples synthesized with the addition of iodine and bromine precursors compared to the pure zinc oxide nanowires. It was also found out that these samples were more sensitive to isopropyl alcohol vapors. A model was proposed to explain the appearance of additional oxygen vacancies in the subsurface layer of the zinc oxide nanowires when sodium iodide or sodium bromide was added to the initial solution. The roles of oxygen vacancies and surface hydroxyl groups in providing the samples with an increased sensitivity were explained. Thus, a method involving the sacrificial doping of zinc oxide nanowires has been developed, which led to an improvement in their gas sensor characteristics due to an increase in the concentration of oxygen vacancies on their surface. The results are promising for percolation gas sensors equipped with additional water vapor traps that work stably in a high humidity.