Localized versus delocalized states: Photoluminescence from electrochemically synthesized ZnO nanowires

We analyze the near-band-edge photoluminescence of electrochemically deposited ZnO nanowires and directly correlate the photoluminescence properties with the carrier concentration in the nanowires as determined from electrochemical impedance spectroscopy. We find a donor density of 8×1019 cm−3 in the as-deposited nanowires and show that the near-band-edge emission results from band-to-band recombination processes (delocalized states). A photoluminescence band centered at 3.328 eV scales with the diameter of the nanowires and is assigned to recombination processes involving surface states. We show that annealing at 500 °C in air reduces the donor density in the nanowires by more than one order of magnitude, leading to sharp excitonic transitions in the electrochemically deposited nanowires.