Ligand field electronic absorption spectroscopy has been applied as a direct probe of Co2+ dopant ions in II-VI based diluted magnetic semiconductor quantum dots. Synthesis of Co2+-doped CdS (Co2+:CdS) quantum dots by simple coprecipitation in inverted micelle solutions has been found to yield predominantly surface bound dopant ions, which are unstable with respect to solvation in a coordinating solvent (pyridine). The solvation kinetics are biphasic, involving two transient intermediates. In contrast, Co2+ ions are doped much more isotropically in ZnS QDs, and this difference is attributed to the similar ionic radii of Co2+ and Zn2+ ions (0.74 Å), as opposed to Cd2+ ions (0.97 Å). We have developed an isocrystalline core/shell synthetic methodology that enables us to synthesize high quality internally doped Co2+:CdS quantum dots. The effect of Co2+ binding on the surface energies of CdS and ZnS quantum dots is discussed and related to the growth mechanism of diluted magnetic semiconductor quantum dots.© (2002) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.