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Investigation of charge transfer in quantum dot (QD) systems is an area of great interest. Specifically, the relationship between capping ligand and rate of charge transfer has been studied as a means to optimize these materials. To investigate the role of ligand interaction on the QD surface for electron transfer, we designed and synthesized a series of ligands containing an electron accepting moiety, naphthalene bisimide (NBI). These ligands differ in their steric bulk: as one allows for π–π stacking between the NBI moieties at high surface coverages, while the other does not, allowing for a direct comparison of these effects. Once grafted onto QDs, these hybrid materials were studied using UV-Vis, fluorescence, and transient absorption spectroscopy. Interestingly, the sample with the fastest electron transfer was not the sample with the most NBI π–π stacking, it was instead where these ligands were mixed amongst oleic acid, breaking up H-aggregates between the NBI groups.
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Oxidation of quantum dots encapsulated in block copolymer micelles as a function of polymer terminal charge
Most high-quality quantum dots (QDs) are synthesized in the organic phase, and are often coated with polymers for use in aqueous biological environments. QDs can exhibit fluorescence losses during phase transfer, but evaluating underlying mechanisms ( e.g. , oxidation, surface etching, loss of colloidal stability) can be challenging because of variation in synthesis methods. Here, fluorescence stability of QDs encapsulated in block co-polymer (BCP) micelles was investigated as a function of BCP terminal functionalization ( i.e. , –OH, –COOH, and –NH 2 groups) and synthesis method ( i.e. , electrohydrodynamic emulsification-mediated selfassembly (EE-SA), sonication, and manual shaking). Fluorescence losses, fluorescence intensity, energy spectra, and surface composition were assessed using spectrofluorometry and cathodoluminescence spectroscopy (CL) with integrated X-ray photoemission spectroscopy (XPS). QDs passivated using charged BCPs exhibited 50–80% lower fluorescence intensity than those displaying neutral groups ( e.g. , –OH), which CL/XPS revealed to result from oxidation of surface Cd to CdO. Fluorescence losses were higher for processes with slow formation speed, but minimized in the presence of poly(vinyl alcohol) (PVA) surfactant. These data suggest slower BCP aggregation kinetics rather than electrostatic chain repulsion facilitated QD oxidation. Thus, polymer coating method and BCP structure influence QD oxidation during phase transfer and should be selected to maximize fast aggregation kinetics.
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- Award ID(s):
- 2011876
- PAR ID:
- 10412248
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 14
- Issue:
- 32
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 11779 to 11789
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2NR00778A
