Photoluminescence Blinking and Reversible Electron Trapping in Copper-Doped CdSe Nanocrystals

Abstract

Single-particle photoluminescence blinking is observed in the copper-centered deep-trap luminescence of copper-doped CdSe (Cu(+):CdSe) nanocrystals. Blinking dynamics for Cu(+):CdSe and undoped CdSe nanocrystals are analyzed to identify the effect of Cu(+), which selectively traps photogenerated holes. Analysis of the blinking data reveals that the Cu(+):CdSe and CdSe nanocrystal "off"-state dynamics are statistically identical, but the Cu(+):CdSe nanocrystal "on" state is shorter lived. Additionally, a new and pronounced temperature-dependent delayed luminescence is observed in the Cu(+):CdSe nanocrystals that persists long beyond the radiative lifetime of the luminescent excited state. This delayed luminescence is analogous to the well-known donor-acceptor pair luminescence of bulk copper-doped phosphors and is interpreted as revealing metastable charge-separated excited states formed by reversible electron trapping at the nanocrystal surfaces. A mechanistic link between this delayed luminescence and the luminescence blinking is proposed. Collectively, these data suggest that electron (rather than hole) trapping/detrapping is responsible for photoluminescence intermittency in these nanocrystals.