Room temperature synthesis of PbSe quantum dots in aqueous solution: stabilization by interactions with ligands

Abstract

An aqueous route of synthesis is described for rapid synthesis of lead selenide quantum dots (PbSe QDs) at room temperature in an attempt to produce water-soluble and stable nanocrystals. Several thiol-ligands, including thioglycolic acid (TGA), thioglycerol (TGC), 3-mercaptopropionic acid (MPA), 2-mercaptoethylamine hydrochloride (MEA), 6-mercaptohexanoic acid (MHA), and l-cysteine (l-cys), were used for capping/stabilization of PbSe QDs. The effects of the ligands on the stability of PbSe QDs were evaluated for a period of two months at room temperature under normal light conditions and at 4 °C in the dark. The TGA- and MEA-capped QDs exhibited the highest stability prior to purification, almost two months when kept in the dark at 4 °C. However, the stability of TGA-capped QDs was reduced substantially after purification to about 5 days under the same conditions, while MEA-capped QDs did not show any significant instability. The stabilization energies of Pb-thiolate complexes determined by theoretical DFT simulations supported the experimental results. The PbSe QDs capped with TGA, MPA and MEA were successfully purified and re-dispersed in water, while those stabilized with TGC, MHA and l-cys aggregated during purification attempts. The purified PbSe QDs possess very susceptible surface resulting in poor stability for about 30-45 min after re-dispersion in water. In the presence of an excess of free ligand, the stability increased up to 5 days for TGA-capped QDs at pH 7.19, 9-12 days for MPA-capped QDs at pH 7.3-7.5 and 45-47 days for MEA-capped QDs at pH 7.35. X-Ray diffraction (XRD) results showed that the QDs possess a cubic rock salt structure with the most intense peaks located at 2θ = 25.3° (200) and 2θ = 29.2° (100). TEM images showed that the size of the QDs ranges between 5 and 10 nm. ICP-MS results revealed that Pb : Se ratios were 1.26, 1.28, 3.85, 1.18, and 1.31 for the QDs capped with TGA, MPA, MEA, l-cys, and TGC, respectively. The proposed method is inexpensive, simple and utilizes environmentally friendly chemicals and solvents.