Role of Pi-Electron Density at the Interface of Small Molecule-Sensitized Solar Cells

Conventional dye-sensitized solar cells (DSSCs) involving charge-transfer interfaces face charge injection losses and offsets for TiO2-sensitizer band alignment. The direct charge-transfer mechanism in DSSCs with catechol (CT, 1,2-benzenediol)-based compounds minimizes the injection losses and eliminates band alignment issues, although the photovoltaic performance of the corresponding device is very poor due to the ultrafast (picosecond) recombination of photoexcited electrons. Just as in a natural photosystem, structural selectivity toward inhibition of this recombination needs to be defined. The interfacial electron density and back electron transfer kinetics at the molecular sensitizer–TiO2 interface play a significant role in the overall energy conversion efficiency. Herein, we identified, for the first time, that the π-electron cloud at the sensitizer–TiO2 interface facilitates the degree of recombination. Comparative density functional theory analyses confirmed that these electron clouds act as large recombination sites. Luminol (LM) and isoluminol (ILM) were employed as “small molecule” sensitizers without the cloud, having a secondary amine linker, which increased the photoenergy conversion efficiency of the single-step sensitization-based photovoltaic cell (type-II DSSC) by reducing the recombination. The device with LM exhibited a power-conversion efficiency (PCE) of ca. 1.11% (representing 363% improvement when compared to CT), the highest ever reported in this category. This understanding is insightful for the design of novel small molecular sensitizers for future DSSCs