Publication date: 15th December 2025
The performance of organic electronic devices, such as solar cells, depends on understanding and controlling the solid-state microstructure of semiconducting polymers. In this presentation, I will discuss our recent understanding of the aggregate states, solid-state microstructure, and thermotropic behavior of the best-performing family of polymers for solar cells, i.e., benzodithiophene-based semiconducting polymers. The following argument will be put forward: that the microstructure of high-performing donor semiconducting polymers does not conform to the traditional structural models developed for polymers, i.e., the amorphous and semi-crystalline models, nor with established polymeric solid mesophases (e.g. vitrified liquid crystals, condis crystals, columnar mesophases, etc.). Instead, these polymers organize into a singular solid mesophase that bears a resemblance to sanidic structures, while concurrently exhibiting characteristics reminiscent of columnar mesophases. Furthermore, recent results on the quantitative analysis of the structural aspects in these materials, using GIWAXS and Ultra-fast chip calorimetry, will be presented. Finally, the discussion will extend to the question of whether these materials exhibit an amorphous phase, as is the case with "regular" polymers.
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