Beyond band alignment: hole localization driven formation of three spatially separated long-lived exciton states in CdSe/CdS nanorods.

Colloidal one-dimensional semiconductor nanoheterostructures have emerged as an important family of functional materials for solar energy conversion, although the nature of the long-lived exciton state and their formation and dissociation dynamics remain poorly understood. In this paper we study these dynamics in CdSe/CdS dot-in-rod (DIR) NRs, a representative of 1D heterostructures, and DIR-electron-acceptor complexes by transient absorption spectroscopy. Because of a quasi-type II band alignment of CdSe and CdS, it is often assumed that there exists one long-lived exciton state with holes localized in the CdSe seed and electrons delocalized among CdSe and CdS. We show that excitation into the CdS rod forms three distinct types of long-lived excitons that are spatially localized in the CdS rod, in and near the CdSe seed and in the CdS shell surrounding the seed. The branching ratio of forming these exciton states is controlled by the competition between the band offset driven hole localization to the CdSe seed and hole trapping to the CdS surface. Because of dielectric contrast induced strong electron-hole interaction in 1D materials, the competing hole localization pathways lead to spatially separated long-lived excitons. Their distinct spatial locations affect their dissociation rates in the presence of electron acceptors, which has important implications for the application of 1D heterostructures as light-harvesting materials.