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We investigate the molecular order and thin film morphology of the conjugated polymer polytellurophene, in order to understand how the tellurium atom and the choice of side-chain influence the conjugated polymer’s backbone planarity and performance in organic transistors. We find that poly(3hexyltellurophene) (P3HTe) continues the trend from polythiophene (P3HT) to polyselenophene (P3HS): substitution with Tellurium leads to a more planar backbone, evident from the shifts of the C═C vibrational peak to lower wavenumbers (∼1389 cm–1) and a smaller optical band gap (∼1.4 eV). Resonant Raman spectroscopy revealed that molecular order was highly dependent on the structure of the P3ATe alkyl side-chain: a longer chains introduces kinetic hindrance, reducing the fraction of ordered phase obtained at room temperature, while a branched side-chain introduces steric hindrance, with intrinsic disorder present even when deposited at higher temperatures. When blended with the insulator HDPE, all three polymers exhibit...

Effects of Side-Chain Length and Shape on Polytellurophene Molecular Order and Blend Morphology