Investigating photoinduced charge transfer in double- and single-emission PbS@CdS core@shell quantum dots

We present for the first time detailed investigation of the charge transfer behavior of PbS@CdS core@shell quantum dots (QDs) showing either a single emission peak from the core or intriguing double emission peaks from the core and shell, respectively. A highly non-concentric core@shell structure model was proposed to explain the origin of double emissions from monodisperse QDs. Their charge transfer behavior was investigated by monitoring photoluminescence (PL) intensity variation with the introduction of electron or hole scavengers. It was found that the PL quenching of the PbS core is more efficient than that of the CdS shell, suggesting more efficient charge transfer from the core to scavengers, although the opposite was expected. Further measurements of the PL lifetime followed by wave function calculations disclosed that the time scale is the critical factor explaining the more efficient charge transfer from the core than from the shell. The charge transfer behavior was also examined on a series of single-emission core@shell QDs with either different core sizes or different shell thicknesses and dominant factors were identified. Towards photovoltaic applications, these PbS@CdS QDs were attached onto multi-walled carbon nanotubes (MWCNTs) and their charge transfer behavior was compared with that in the PbS-QD/MWCNT system. Results demonstrate that although the CdS shell serves as an electron transfer barrier, the electrons excited in the PbS cores can still be transferred into the MWCNTs efficiently when the shell thickness is similar to 0.7 nm. Considering their higher stability, these core@shell QDs are very promising for the development of highly efficient QD-based photovoltaic devices.