Redox-Inactive CO Determines Atmospheric Stability of Electrical Properties of ZnO Nanowire Devices through a Room-Temperature Surface Reaction.

Emerging interactive electronics for the Internet of Things era inherently require the long-term stability of semiconductor devices exposed to air. Nanostructured metal oxides are promising options for such atmospherically stable semiconductor devices owing to their inherent stability in air. Among various oxide nanostructures, ZnO nanowires have been the most intensively studied for electrical and optical device applications. Here, we demonstrate a strategy for achieving the atmospheric electrical stability of ZnO nanowire devices. Although the chemically active oxygen and water in air are strong candidates for affecting the electrical stability of nanoscale metal oxides, we found that the ppm-level redox-inactive CO in air critically determines the atmospheric electrical stability of hydrothermally grown single-crystalline ZnO nanowires. A series of analyses using atmosphere-controlled electrical characterization of single nanowire devices, Fourier transform infrared spectroscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy consistently revealed that atmospheric CO reacts substantially with the ZnO nanowire surfaces, even at room temperature, to form an electrically insulative zinc carbonate thin layer. The formation of this layer essentially limits the atmospheric electrical stability of the ZnO nanowire devices. Based on this surface carbonation mechanism, we propose a strategy to suppress the detrimental surface reaction, which is based on (1) reducing the density of surface hydroxyl groups and (2) improving the nanowire crystallinity by thermal pretreatment. This approach improves the atmospheric electrical stability to at least 40 days in air.