The Effect of H‐ and J‐Aggregation on the Photophysical and Photovoltaic Properties of Small Thiophene–Pyridine–DPP Molecules for Bulk‐Heterojunction Solar Cells

The performance of organic semiconductors in optoelectronic devices depends on the functional properties of the individual molecules and their mutual orientations when they are in the solid state. The effect of H‐ and J‐aggregation on the photophysical properties and photovoltaic behavior of four electronically identical but structurally different thiophene–pyridine–diketopyrrolopyrrole molecules is studied. By introducing and changing the position of two hexyl side chains on the two peripheral thiophene units of these molecules, their aggregation in thin films between H‐type and J‐type is effectively tuned, as evidenced from the characteristics of optical absorption, fluorescence, and excited state lifetime. The two derivatives that assemble into J‐type aggregates exhibit a significantly enhanced photovoltaic performance, up to an order of magnitude, compared to the two molecules that form H‐type aggregates. The reasons for this remarkably different behavior are discussed. The aggregation behavior of electronically identical thiophene–pyridine–diketopyrrolopyrrole molecules is modulated by introducing and modifying the position of two hexyl side chains on the peripheral thiophene rings. Improved photovoltaic performance is achieved for those molecules assembling into J‐type aggregates in contrast to those forming H‐aggregates as a result of a faster charge generation and a reduced bimolecular recombination.