Conversion of InP Clusters to Quantum Dots.

Understanding and deconvoluting the different mechanisms involved in the synthesis of nanomaterials is necessary to make uniform materials with desirable function. In this study, in situ spectroscopic methods were used to study exchange reactions at the surface of indium phosphide clusters, revealing that the cluster surface lacks significant dynamics on the NMR time-scale at room temperature. The exchange of surface carboxylate ligands can be induced at elevated temperatures and with the addition of carboxylic acid and indium carboxylate. These studies suggest that carboxylate may be a key ingredient in promoting cluster dissolution to larger nanostructures. Toward this end, the evolution of InP clusters was examined by in situ UV-vis spectroscopy, revealing cluster dissolution and renucleation that is dramatically dependent on the concentration of carboxylate. In addition to the concentration of exogenous ligands, the rate of particle growth and final product distribution were dependent on temperature and initial cluster concentration. These results, taken together, suggest a mechanism of cluster evolution involving cluster dissociation to form multiple reactive monomer species that renucleate and grow to larger nanomaterials. Nonproductive monomer degradation is observed in the lower temperature regime (<200 °C), suggesting a critical temperature threshold for efficient cluster to quantum dot conversion.