Quasi-Type II Carrier Distribution in CdSe/CdS Core/Shell Quantum Dots with Type I Band Alignment

Band alignments are essential for understanding the optical properties and carrier transfer of core/shell QDs. As CdSe/CdS core/shell QDs with increasing shell thickness represent red shifted absorption and luminescence spectra, weakened oscillator strength of the lowest electronic transition, and elongated luminescence lifetime, they are assigned to quasi-type II band alignment. However, femtosecond transient absorption spectroscopy with state-selective excitation revealed a type I band alignment of the CdSe/CdS QDs with a thin CdS shell, in which the excited electron is localized in the CdSe core with core excitation while delocalized in the whole QDs with shell excitation, even though a quasi-type II carrier distribution was observed with steady-state spectroscopy. In the type I core/shell QDs, the CdS shell acts as an energy barrier in surface electron and hole-trapping processes. The time constant of the hole-trapping process of the CdSe core (similar to 10 ps) was elongated 10 times owing to a tunnel effect through the high energy barrier of the CdS shell, which was estimated from the decay related to the biexcitonic induced spectral shift. The biexcitonic spectral shift induced by a,similar to 100 ps hole-trapping process was also observed at the 1S(e)-2S(3/2)(h) transition. Our results from transient absorption spectroscopy with state-selective excitation are useful to clarify band alignment and carrier distribution of hetero-nanostructures, which could help to objectively extract charge carriers in photovoltaic applications.