This paper reports experimental studies of the development of bulk optical properties as a function of crystallite size for the inorganic direct gap semiconductor CdS. Small crystallites are synthesized via colloidal chemical techniques, and their optical properties are studied in situ at extreme dilution. The crystallites are characterized via high resolution transmission electron microscopy. Direct images show (111) lattice planes, and establish the crystallite structures as close to those of excised fragments of bulk CdS (zinc-blende cubic). Large crystallites (> 100 Å average diameter) show an optical absorption, in colloidal solution, close to that of bulk crystalline material. However, small crystallites of 30 Å average diameter show a large blue shift (∼0.8 eV) in absorption edge (effective band gap), and an intensification of edge absorption relative to absorption at higher energy regions. These observations can be understood as quantum size effects resulting from confinement of an electron and hole in a small volume. 40 Å average size crystallites show a smaller shift (∼0.25 eV), and corresponding changes in their fluorescence, and resonance Raman excitation, spectra.

We present the basis for an entirely new approach to in situ nanoparticle sizing. Nanoparticles containing just 12 zeptomoles (1 zeptomole = 10(-21) moles) of silver, are detected via in situ particle coulometry. These stochastic charge measurements correspond to the transfer of only 7000-8000 electrons, yielding direct information relating to the individual nanoparticle volumes. The resulting particle size distribution (average equivalent radius 5 nm) obtained via nanoparticle coulometry is in excellent correspondence with that attained from TEM analysis. Moreover, the measurable particle size limit by this electrochemical method is shown to be significantly below that of more common optical nanoparticle tracking techniques, and as such can be viewed as a potential disruptive nano-technology.

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