Extremely long-lived charge donor states formed by visible irradiation of quantum dots

23 April 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Using cyclic voltammetry under illumination, we recently demonstrated that CdS quantum dots (QDs) form charge donor states that live for at least several minutes after illumination ends, ~12 orders of magnitude longer than expected for free carriers. This timescale suggests that the conventionally accepted mechanism of charge transfer, wherein charges directly transfer to an acceptor following exciton dissociation, cannot be complete. Because of these long timescales, this unconventional pathway is not readily observed using time-resolved spectroscopy to probe charge transfer dynamics. Here, we investigated the chemical nature of these charge donor states using cyclic voltammetry under illumination coupled with NMR spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and optical spectroscopy. Our data reveal that charges are stored locally rather than as free carriers, and the number of charges stored is dependent on the QD surface ligation and stoichiometry. Altogether, our results confirm that electrons are stored at ligated surface Cd, these sites are competent charge donors, and this storage is charge balanced by X-type ligand desorption. We found that charge storage occurs in every QD system studied, including CdS, CdSe, and InP capped with carboxylate and phosphonate ligands.


charge transfer
quantum dot
charge storage
cyclic voltammetry

Supplementary materials

Supporting Information
Additional experimental details, data processing and calculations, alternative mechanism discussion, and supplementary data.


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