The electron injection rate in CdSe quantum dot sensitized solar cells: from a bifunctional linker and zinc oxide morphology

Herein, we have investigated the effect of both the bifunctional linker (L1, L2, L3, and L4) and ZnO morphology (porous nanoparticles (NPs), nanowires (NWs), and nanotubes (NTs-A and NTs-Z)) on the electron injection in CdSe QD sensitized solar cells by first-principles simulation. Via calculating the partitioned interfaces formed by different components (linker/QDs and ZnO/linker), we found that the electronic states of QDs and every ZnO substrate are insensitive to any linker, while the frontier orbitals of L1-L4 (with increased delocalization) manifest a systematical negative-shift. Because of the lowest unoccupied molecular orbital (LUMO) of L1 compared to its counterparts aligned in the region of the virtual states of QDs or the substrate with a high density of states, it always yields a stronger electronic coupling with QDs and varied substrates. After characterization of the complete ZnO/linker/QD system, we found that the electron injection time (τ) vastly depends on both the linker and substrate. On the one hand, L1 bridged QDs and every substrate always achieve the shortest τ compared to their counterpart associated cases. On the other hand, NW supported systems always yield the shortest τ no matter what the linker is. Overall, the NW/L1/QD system achieves the fastest injection by ∼160 fs. This essentially stems from the shortest molecular length of L1 decreasing the distance between QDs and the substrate, subsequently improving the interfacial coupling. Meanwhile, the NW supported cases generate the less sensitive virtual states for both the QDs and NWs, ensuring a less variable interfacial coupling. These facts combined can provide understanding of the effects contributed from the linker and the oxide semiconductor morphology on charge transfer with the aim of choosing an appropriate component with fast directional electron injection.