A microscopic picture of surface charge trapping in semiconductor nanocrystals

摘要

The current model for understanding trapping of charge carriers to the surface of semiconductor nanocrystals is inconsistent with experimental evidence indicating that carriers can thermally de-trap from surface sites. A proper understanding of the microscopic details of charge trapping would guide chemical design of the nanocrystal surface for applications such as charge transport, sensing, or photochemistry. This thesis presents a model of surface charge trapping in which transitions to surface state are governed by rates derived from semiclassical electron-transfer theory. In this picture, trapping to the surface induces a strong polarization in the nanocrystal, resulting in a trapped state with strong electron-phonon coupling via the Frölich mechanism. This trapped state then emits over a broad energy range due to a Franck-Condon vibronic progression. This model is shown to be consistent with the temperature-dependence of core and surface emission as well as the spectral properties of surface emission. The strong coupling of the surface state is validated by independent experiments, and the model is shown to hold promise for explaining the experimental data regarding the trapping of hot (excess energy) carriers.