Surface defects on ZnO nanowires: implications for design of sensors

Surface defects are commonly believed to be fundamentally important to gas-sensor performance. We examine the effect of gas coverage and ethanol orientation on its adsorption on the stoichiometric and oxygen deficient (10 (1) over bar0) nanowire surface. Our density functional theory calculations show that ethanol adsorbs in multiple stable configurations at coverages between 1/4 and 1 ML, highlighting the ability of ZnO to detect ethanol. Ethanol prefers to bind to a surface Zn via the adsorbate oxygen atom and, if a surface oxygen atom is in close proximity, the molecule is further stabilized by formation of a hydrogen bond between the hydrogen of the hydroxyl group and the surface oxygen. Two primary adsorption configurations were identified and have different binding strengths that could be distinguished experimentally by the magnitude of their OH stretching frequency. Our findings show that ethanol adsorbed on the oxygen deficient ZnO(10 (1) over bar0) surface has a reduced binding strength. This is due to either the lack of a hydrogen bond (due to a deficiency in surface oxygen) or to surface reconstruction that occurs on the defect surface that weakens the hydrogen bond interaction. This reduced binding on the oxygen deficient surface is in contrast to the defect enhanced gas-sensor interaction for other gases. Despite this difference, ethanol still acts as a reducing gas, donating electrons to the surface and decreasing the band gap. We show that multiple adsorbed ethanol molecules prefer to be orientated parallel to each other to facilitate the hydrogen bonding to the defect-free surface for enhanced interaction.