Dependence of the final-state effect on the coupling between a CdSe nanoparticle and its neighbors studied with photoemission spectroscopy

Abstract

A simple model based on an electrostatic calculation of the photoemission effect in the final state is used to characterize the energy shift, relative to bulk material, which is dependent on size in the photoemission spectra of organically passivated CdSe nanoparticles (NPs). For trioctylphosphine oxide/hexadecylamine-passivated NPs, the core-level shifts are well described with a model involving a static effect in the final state. After the NPs are treated with pyridine, the energy shifts are smaller; this decrease is ascribed to a dynamic effect in the final state describing a finite lifetime, on a femtosecond scale, of the photohole residing in the NP. This condition is intimately related to the coupling between the NP and metallic substrate and among NPs themselves. For the valence-band edge, an additional effect of the initial state due to quantum confinement is required to elucidate the energy shift. We find that this initial-state shift is smaller than a prediction according to a semiempirical pseudopotential calculation.