Defect-promoted photo-electrochemical performance enhancement of orange-luminescent ZnO nanorod-arraysElectronic supplementary information (ESI) available. See DOI: 10.1039/c7cp01606a

Intentionally defect-rich zinc oxide (ZnO) nanorod-arrays were grown from solution by carefully adjusting the concentration ratio of the growth-precursors used followed by various post-deposition thermal treatments. Post-deposition rapid thermal annealing (RTA) at moderate temperatures (350 °C-550 °C) and in various atmospheres was applied to vary the defect composition of the grown nanorod-arrays. It is demonstrated that, intense, defect-related orange emission occurs solely upon RTA around 450 °C and is essentially independent of the atmosphere used. Extensive materials characterization was carried out in order to evaluate the origin of the orange-luminescent defects and what influence they have on the ZnO material properties. It is concluded that the oxygen vacancy-zinc interstitial defect complex (V O -Zn i ) is responsible for the orange luminescence in the prepared materials. A kinetic formation mechanism of the V O -Zn i complex dependent on the RTA temperature is proposed and shown to be in accordance with the experimental findings. Furthermore it is shown that this bulk deep-level defect could act as a trap state for photo-generated electrons prolonging the charge carrier lifetime of photo-generated holes and therefore improving the charge carrier separation in the material. As a result the photo-current density under simulated sunlight is found to increase by almost 150% over as-grown samples. The potential use of this defective material in applications such as solar water splitting is outlined. Defect engineering in ZnO: origin of strong orange-luminescent defects in solution-grown nanorod-arrays and their enhanced photo-electrochemical performance.