Rationalization of the light-induced electron injection mechanism in a model 1D ZnO nanowire-dye complex: insights from real-time TD-DFTB simulations

Abstract

Zinc oxide nanowires (ZnO NWs) possess a unique one-dimensional (1D) morphology that offers a direct pathway for charge transport. In this article, we present the first application of the real-time time-dependent density functional tight-binding (real-time TD-DFTB) method for a model hybrid system consisting of a catechol molecule adsorbed on a ZnO nanowire. The rationalization of the photoinduced electron injection to the 1D nanostructure is attained through quantum dynamics simulations, stressing the role of charge transfer in the new optical transitions upon dye adsorption. We provide a momentum-resolved picture of the photoexcitation dynamics, highlighting the charge accumulation in certain k-points, which could improve our understanding of these ultrafast processes. Finally, in the context of dye-sensitized solar cells (DSSCs) based on ZnO NW arrays, we provide a method to calculate the photoresponse obtaining similar results to experiments. This work paves the way towards the fast and accurate theoretical design of 1D optoelectronic nanodevices.