A Reduction Pathway in the Synthesis of PbSe Nanocrystal Quantum Dots

Abstract

Colloidal nanocrystal quantum dots (NQDs) of narrow band gap materials are of substantial general interest because of their unparalleled potential as infrared fluorophores. While PbSe NQDs are a promising class of infrared-active nanocrystals due to high emission quantum yields and a wide useful spectral range, typical synthetic methods are sensitive to a variety of factors, including the influence of solvent/ligand impurities that render reproducibility difficult. In this work, we specifically examine the effects of diphenylphosphine and 1,2-hexadecanediol, as surrogates for putative trioctylphosphine-based reducing impurities, on the synthesis of PbSe NQDs. Specifically, we compare their influence on NQD size, chemical yield, and photoluminescence quantum yield. While both additives substantially increase the chemical yield of the synthesis, they demonstrate markedly different effects on emission quantum yield of the product NQDs. We further examine the effects of reaction temperature and oleic acid concentration on the diol-assisted synthesis. Increased oleic acid concentration led to somewhat higher growth rates and larger NQDs but at the expense of lower chemical yield. Temperature was found to have an even greater effect on growth rate and NQD size. Neither temperature nor oleic acid concentration was found to have noticeable effects on NQD emission quantum yield. Finally, we use numerical simulations to support the conjecture that the increased yield is likely a result of faster monomer formation, consistent with the activation of an additional reaction pathway by the reducing species.