Cluster generation under pulsed laser ablation of zinc oxide

Neutral and cationic ZnnOm clusters of various stoichiometry have been produced by nanosecond laser ablation of ZnO in vacuum and investigated by time-of-flight mass spectrometry. Particular attention was paid to the effect of laser wavelength (in the range from near-IR to UV) on cluster composition. Under 193-nm laser ablation, the charged clusters are essentially substoichiometric with \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\mathrm{Zn}_{n}\mathrm{O}_{n-1}^{+}$\end{document} and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\mathrm{Zn}_{n}\mathrm{O}_{n-3}^{+}$\end{document} being the most abundant series. Both sub- and stoichiometric cationic clusters are generated in abundance at 532- and 1064-nm ablation whose composition depends on the cluster size. The reactivity of small stoichiometric \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\mathrm{Zn}_{n}\mathrm{O}_{n}^{+}$\end{document} clusters (n<11) toward hydrogen is found to be high, while oxygen-deficient species are less reactive. The neutral plume particles are mainly stoichiometric with Zn4O4 tetramer being a magic cluster. It is suggested that the Zn4O4 loss is the dominant fragmentation channel of large zinc oxide clusters upon electron impact. Plume expansion conditions under ZnO ablation with visible and IR laser pulses are shown to be favorable for stoichiometric cluster formation.