The field of organic electronics has witnessed major developments recently that have led to vastly improved charge transport and energy-harvesting properties of these systems. This progress can be predominantly attributed to synthetic efforts in the creation of new materials, that often exhibit significantly more rigid backbones than the first-generation polymer semiconductors. These more rigid backbone polymers require much larger solubilizing side-chains, thus coined “hairy-rod” polymers. However, the structure-property interrelations of hairy-rod polymers are not well understood, due to their limited long-range order and weakly resolved thermal transitions, among which is side-chain ordering. We use thermoanalytical techniques on a series of increasingly more rigid backbone polymers to provide insight into side-chain ordering kinetics and thermodynamics, including nucleation affects from already formed backbone crystals. These side-chains are ordered in an extended-chain-like conformation that affects kinetic and thermal properties, specifically phase transition and degree of crystallinity in comparison to folded-chain crystals. This work provides insight to understanding the side-chain softening regime of hairy-rod polymers, which, in turn, provides a basis to further unravel the structure-property relations of hairy-rod polymers.

Influence of side-chains on thermal and kinetic properties in hairy rod polymers

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