Semiconductor cluster beams: One and two color ionization studies of Si<i>x</i> and Ge<i>x</i>

Supersonic beams of clusters of Si and Ge atoms have been produced by laser vaporization followed by supersonic expansion in a helium carrier. The cluster beams were characterized by F2(7.9 eV) and ArF(6.4 eV) excimer laser ionization accompanied by time-of-flight mass analysis. In addition, the feasibility of a resonant two-photon ionization (R2PI) spectroscopic study was explored by two-color experiments involving initial excitation with the second (2.36 eV) and third (3.54 eV) harmonics of the Nd:YAG followed by excimer laser ionization. All two-photon ionization processes were found to produce extensive fragmentation of the larger clusters. The observed fragmentation pattern for the silicon and germanium clusters were remarkably similar to each other, but drastically different from that seen for metal clusters in the same apparatus. Unlike metal clusters, which tend to lose one atom at a time, these semiconductor clusters appear to fragment by a fission process, the daughter ions falling almost exclusively in the size range from 6 to 11 atoms. Time delay studies in the two-color experiments established that clusters of both Si and Ge have excited electronic states with lifetimes of approximately 100 ns. This again is dramatically different from the behavior found with metal clusters, and indicates the feasibility of R2PI spectroscopy on these cold semiconductor particles. The existence of such long-lived excited states indicates that there is probably an energy gap between the band of electronic states being excited and the ground electronic state.