Self-assembly of only one functionalized porphyrin dye molecule with one CdSe/ZnS quantum dot (QD) not only modifies the photoluminescence (PL) intensity but also creates a few energetically clearly distinguishable electronic states, opening additional effective relaxation pathways. The related energy modifications are in the range of 10-30 meV and show a pronounced sensitivity to the specific nature of the respective dye. We assign the emerging energies to surface states. Time-resolved PL spectroscopy in combination with spectral deconvolution reveals that surface properties of QDs are a complex interplay of the nature of the dye molecule and the topography of the ligand layer across a temperature range from 77 to 290 K. This includes a kind of phase transition of trioctylphosphine oxide ligands, switching the nature of surface states observed below and above the phase transition temperature. Most importantly, our findings can be closely related to recent calculations of ligand-induced modifications of surface states of QDs. The identification of the optical properties emerged from a combination of spectroscopy on single QDs and QDs in an ensemble.
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