Observation of Electron Shakeup in CdSe/CdS Core/Shell Nanoplatelets

While ensembles of CdSe nanoplatelets (NPLs) show remarkably narrow photoluminescence line widths at room temperature, adding a CdS shell to increase their fluorescence efficiency and photostability causes line width broadening. Moreover, ensemble emission spectra of CdSe/CdS core/shell NPLs become strongly asymmetric at cryogenic temperatures. If the origin of these effects were understood, this could potentially lead to stable core/shell NPLs with narrower emission, which would be advantageous for applications. To move in this direction, we report time-resolved emission spectra of individual CdSe/CdS core/shell NPLs at 4 K. We observe surprisingly complex emission spectra that contain multiple spectrally narrow emission features that change during the experiment. With machine-learning algorithms, we can extract characteristic peak energy differences in these spectra. We show that they are consistent with electron "shakeup lines" from negatively charged trions. In this process, an electron-hole pair recombines radiatively but gives part of its energy to the remaining electron by exciting it into a higher single-electron level. This "shakeup" mechanism is enabled in our NPLs due to strong exciton binding and weak lateral confinement of the charge carriers. Time-resolved single-photon-counting measurements and numerical calculations suggest that spectral jumps in the emission features originate from fluctuations in the confinement potential caused by microscopic structural changes on the NPL surface (e.g., due to mobile surface charges). Our results provide valuable insights into line width broadening mechanisms in colloidal NPLs.