Dynamic distribution of growth rates within the ensembles of colloidal II-VI and III-V semiconductor nanocrystals as a factor governing their photoluminescence efficiency

The distribution of properties within ensembles of colloidally grown II-VI and III-V semiconductor nanocrystals was studied. A drastic difference in the photoluminescence efficiencies of size-selected fractions was observed for both organometallically prepared CdSe and InAs colloids and for CdTe nanocrystals synthesized in aqueous medium, indicating a general character of the phenomenon observed. The difference in the photoluminescence efficiencies is attributed to different averaged surface disorder of the nanocrystals originating from the Ostwald ripening growth mechanism when larger particles in the ensemble grow at the expense of dissolving smaller particles. At any stage of growth, only a fraction of particles within the ensemble of growing colloidal nanocrystals has the most perfect surface and, thus, shows the most efficient photoluminescence. This is explained by a theoretical model describing the evolution of an ensemble of nanocrystals in a colloidal solution. In an ensemble of growing nanocrystals, the fraction of particles with the highest photoluminescence corresponds to the particle size having nearly zero average growth rate. The small average growth rate leads to the lowest possible degree of surface disorder at any given reaction conditions.