Controlling the oxidation processes of Zn nanoparticles produced by pulsed laser ablation in aqueous solution

We used online UV-VIS optical absorption and photoluminescence spectra, acquired during and after pulsed laser ablation of a Zinc plate in aqueous solution, to investigate the effect of the laser repetition rate and liquid environment on the oxidation processes of the produced nanoparticles. A transient Zn/ZnO core-shell structure was revealed by the coexistence of an absorption peak around 5.0 eV due to Zn surface plasmon resonance and of an edge at 3.4 eV coming from wurtzite ZnO. The growth kinetics of ZnO at the various repetition rates, selectively probed by the excitonic emission at 3.3 eV, began immediately at the onset of laser ablation and was largely independent of the repetition rate. In addition, we detected an emission at 2.3 eV related to oxygen vacancies, which began to grow after a number of pulses increasing with the used repetition rate. Optical absorption spectra during and after ablation in a mixture of water and ethanol (0%-100%) revealed that the oxidation kinetics of Zn nanoparticles slows down from about 900 s in pure water to at least one week in pure ethanol.