Crystal defects in unintentionally doped ZnO nanowires grown by chemical bath deposition (CBD) play a capital role on their optical and electrical properties, governing the performances of many nanoscale engineering devices. However, the nature of these crystal defects is still highly debated. In particular, the hydrogen-related defects have not been explored in detail yet although the growth medium operates in aqueous solution. By using four-point probe resistivity measurements, we show that ZnO nanowires grown by CBD using zinc nitrate and hexamethylenetetramine exhibit a high electrical conductivity with electron densities ranging from 2.7 x 10 18 to 3.1 x 10 19 cm -3 . Most of them have a metallic electrical conduction. By combining density-functional theory calculations with cathodoluminescence and Raman spectroscopy, we reveal that the high electrical conductivity mostly originates from the formation of interstitial hydrogen in bond-centered sites (HBC) and of zinc vacancy -hydrogen (VZn-nH) complexes. In particular, the HBC and (VZn-3H) complex are found to act as two shallow donors with a very low formation energy, for which the most stable configurations are reported. Additionally, this combined theoretical and experimental approach allows us to revisit the highly debated origin of the visible and ultra-violet emission bands in the luminescence spectra. They are found to be mostly related to VZn and (VZn-nH) complexes located in the bulk and on the surfaces of ZnO nanowires. These findings represent an important step forward in the identification of the predominant native and extrinsic defects driving the electronic structure properties of ZnO nanowires grown by CBD. They further reveal the significance of hydrogen engineering to tune the source of crystal defects for optimizing the physical properties of ZnO nanowires.
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