Modeling materials and processes in dye-sensitized solar cells: understanding the mechanism, improving the efficiency.

We present a review of recent first-principles computational modeling studies on dye-sensitized solar cells (DSCs), focusing on the materials and processes modeling aspects which are key to the functioning of this promising class of photovoltaic devices. Crucial to the DSCs functioning is the photoinduced charge separation occurring at the heterointerface(s) between a dye-sensitized nanocrystalline, mesoporous metal oxide electrode and a redox shuttle. Theoretical and computational modeling of isolated cell components (e.g., dye, semiconductor nanoparticles, redox shuttle, etc…) as well as of combined dye/semiconductor/redox shuttle systems can successfully assist the experimental research by providing basic design rules of new sensitizers and a deeper comprehension of the fundamental chemical and physical processes governing the cell functioning and its performances. A computational approach to DSCs modeling can essentially be cast into a stepwise problem, whereby one first needs to simulate accurately the individual DSCs components to move to relevant pair (or higher order) interactions characterizing the device functioning. This information can contribute to enhancing further the target DSCs characteristics, such as temporal stability and optimization of device components. After presenting selected results for isolated dyes, including the computational design of new dyes, and model semiconductors, including realistic nanostructure models, we focus in the remainder of this review on the interaction between dye-sensitizers and semiconductor oxides, covering organic as well as metallorganic dyes.