Indoline-Based Molecular Engineering for Optimizing the Performance of Photoactive Thin Films

New indoline dyes (RK‐1–4) were designed with a planar geometry and high molar extinction coefficient, which provided surprising power conversion efficiency (PCE) with a thin titanium dioxide film in dye‐sensitized solar cells (DSCs). They had a difference in only alkyl chain length. Despite the same molecular structure, the performance of the respective DSCs varied significantly. Investigating the dye adsorption processes and charge transfer kinetics, the alkyl chain length was determined to affect the dye surface coverage as well as the recombination between the injected photoelectrons and the oxidized redox mediators. When applied to the DSCs as a light harvester, RK‐3 with the dodecyl group exhibited the best photocurrent density, consequently achieving the best PCE of 9.1% with a 1.8 μm active and 2.5 μm scattering layer because of the most favorable charge injection. However, when increasing the active layer thickness, overall device performance deteriorated and the charge collection and regeneration played major roles for determining the PCE. Therefore, RK‐2 featuring the highest surface coverage and moderate alkyl chain length obtained the highest PCEs of 8.8% and 7.9% with 3.5 and 5.1 μm active layers, respectively. These results present a promising perspective of organic dye design for thin film DSCs. New indoline derivatives characterized by good planarity and high molar absorptivity are successfully applied to dye‐sensitized solar cells (DSCs). By controlling the hydrocarbon chain length, noticeable photocurrent density is achieved at a very thin TiO2 film, which is traced elementally, guiding the research of organic dyes for thin film‐based DSCs.