Quasicrystalline and crystalline rare-gas clusters produced in supersonic jets: Impact of the jet clustering level on cathodoluminescence spectra

The paper proposes a new approach to studying cathodoluminescence spectra of substrate-free rare-gas clusters produced in supersonic jets exhausting into a vacuum. The approach, which takes into account the fraction of the clustered substance in the jet, is applied to quantitatively analyze integrated intensities of the luminescence bands of the neutral and charged excimer complexes (Rg2)* and (Rg4+)* measured for nanoclusters of three rare gases (Rg = Ar, Kr, and Xe) with average sizes ranging from 100 to 18000 atoms per clusters (diameters varying from 2 to 13 nm). The amount of the clustered substance, which affects the absolute values of integrated intensity of the bands, is shown to be proportional to the logarithm of the average size of clusters in the jet. Analysis of normalized intensities allowed us to spectroscopically find two ranges of average sizes of Ar, Kr, and Xe nanoclusters which, in accordance with the electron diffraction studies, can be assigned to quasicrystalline icosahedral and crystalline fcc structures in clusters, as well as to find the cluster size range in which both structures coexist. We show that in fcc clusters the luminescence of the neutral molecules (Rg2)* comes from within the volume of the cluster, while the charged excimer complexes (Rg4+)* emit mostly from subsurface layers.