We have used synchrotron radiation photoemission to probe the valence and core level electronic structure of compound-semiconductor monodisperse clusters (nanocrystals). These clusters exhibited a 10% or less variation relative to the mean diameter and were attached to the metal substrates via alkane chains. Direct evidence of gap broadening due to size variation in CdS clusters was observed. The novel utilization of alkane chain attachment is the key to eliminating the otherwise debilitating problem of sample charging, as occurs with powders. The quality of sample preparation was confirmed by other methods such as transmission electron microscopy, Raman scattering, and x-ray diffraction. This work provides a direct link between photoemission studies of expitaxial ultrathin films of compound semiconductors, the photon-spectroscopy measurements of cluster powders and the existing theories of quantum confinement in reduced dimensionality structures.
