We have studied the formation of molecular scale particles or “clusters” of alkali halides and semiconductors during laser vaporization of solids. By measuring the abundances of cluster ions produced in several different source configurations, we have determined that clusters are ejected directly from the source sample and do not need to grow from atomic or molecular vapor. Using samples of mixed alkali halide powders, we have found that unalloyed clusters are easily produced in a source that prevents growth from occurring after the clusters leave the sample surface. However, melting the sample or encouraging growth after vaporization lead to the production of alloyed cluster species.
The sizes of the ejected clusters are initially random, but the population spectrum quickly becomes structured as hot, unstable-sized clusters decay into smaller particles. In carbon, large clusters with odd numbers of atoms decay almost immediately. The hot even clusters also decay, but much more slowly. The longest lived clusters are the magic C50 and C60 fullerenes. The mass spectrum of large carbon clusters evolves in time from structureless, to only the even clusters, to primarily C50 and C60. If cluster growth is encouraged, the odd clusters reappear and the population spectrum again becomes relatively structureless.
The laser vaporization process in non-metallic systems closely resembles multiphoton laser photodissociation of clusters themselves. As a result, the best cluster source samples are powders or powder-like materials. We have found that carbon powder or exfoliated graphite sheet (Union Carbide Grafoil) are the best samples for the production of large carbon clusters. Many previous studies of carbon clusters formed in vacuum may have relied on the vaporization of carbon dust produced by repeated vaporizations in a small region of the sample.