Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
DOI: https://doi.org/10.29363/nanoge.matsusfall.2024.136
Publication date: 28th August 2024
It is knonw that the ratio of ordered/disordered domains in thin films has a direct impact on the doping extent and doping kinetics of semiconducting polymers.[1] By combining ether side chain engineering and uniaxial alignment, we present an effective strategy to finely control the film morphology, leading to unprecedented performance in thermoelectric applications (OTEs) and organic electrochemical transistors (OECTs). In this contribution, we demonstrate in particular the potential of novel single ether side chains to substitute standard alkyl side chains and offer a viable alternative to oligo(ethylene glycol) side chains for the design of high-performing doped materials. Single ether side chains are simple to synthesis and air stable. The enhancement of polarity facilities dopant insertion, while maintaining high thermomechanical cohesion to afford highly oriented films. The resulting films made of PBTTT-8O – PBTTT with single ether side chains with the ether function in the 8th position - delivered record electrical conductivities, reaching 50 000 S cm‑1 upon chemical doping with F6TCNNQ for OTEs[2] and reversible 2 700 S cm‑1 upon electrochemical doping in OECTs in aqueous KPF6 electrolyte.[3] To rationalize these improvements, we studied four polymers bearing single ether side chains with various position of the ether function (x = 3, 5, 8, 11) and compared them to the reference alkyl PBTTT-C12. We found clear dependences of the position of the ether function on the thermo-structural behavior of PBTTT-xO polymers and their resulting crystallinity index.[4] We present here how these trends can be exploited to finely tune the doping properties of polymers and their OTE performance. To conclude, we will introduce two new PBTTTs including two and four ether functions along the side chains and investigate how OECT kinetic and transconductance are evolving as compared to single ether side-chains based PBTTTs. This study aims at improving our current understanding on how introducing heteroatoms along side chains impacts polymer organization and dopant accommodation for future generations of polar side chains.
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