Dopant-Induced Shape Evolution of Colloidal Nanocrystals: The Case of Zinc Oxide

The electrical, optical and other important properties of colloidal nanocrystals are determined mainly by the crystals' chemical composition, size and shape. The introduction of specific dopants is a general approach of modifying the properties of such nanocrystals in well-controlled ways. Here we show that in addition to altering the atomic composition of the nanocrystals the introduction of specific dopants can also lead to dramatic changes in morphology. The creation of Mg-doped ZnO nanocrystals provides an excellent example of this procedure; depending on the molar ratio of dopant precursor in the reagents, doped nanocrystals with well-defined shapes, from tetrapods to ultrathin nanowires, which exhibit tunable optoelectronic properties, are obtained for the first time. We find that the Mg dopants play an important role in the primary growth stage, resulting in initial growth seeds having diverse crystallographic structures, which are critical for the generation of doped nanocrystals with different shapes. We demonstrate that this "greener" synthetic scheme can be extended to other dopant systems and provides an attractive and effective strategy for fabricating doped ZnO nanocrystals with interesting compositional and spatial complexity.