The pH-dependent photoluminescence of colloidal CdSe/ZnS quantum dots with different organic coatings

The photoluminescence (PL) of colloidal quantum dots (QDs) is known to be sensitive to the solution pH. In this work we investigate the role played by the organic coating in determining the pH-dependent PL. We compare two types of CdSe/ZnS QDs equipped with different organic coatings, namely dihydrolipoic acid (DHLA)-capped QDs and phospholipid micelle-encapsulated QDs. Both QD types have their PL intensity quenched at acidic pH values, but they differ in terms of the reversibility of the quenching process. For DHLA-capped QDs, the quenching is nearly irreversible, with a small reversible component visible only on short time scales. For phospholipid micelle-encapsulated QDs the quenching is notably almost fully reversible. We suggest that the surface passivation by the organic ligands is reversible for the micelle-encapsulated QDs. Additionally, both coatings display pH-dependent spectral shifts. These shifts can be explained by a combination of irreversible processes, such as photo-oxidation and acid etching, and reversible charging of the QD surface, leading to the quantum-confined Stark effect (QCSE), the extent of each effect being coating-dependent. At high ionic strengths, the aggregation of QDs also leads to a spectral (red) shift, which is attributable to the QCSE and/or electronic energy transfer.