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Conjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well-understood strategies exist to further advance their thermoelectric performance. Here a new model system is reported for a better understanding of the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods, the effect of controlled incorporation of tie-chains between the crystalline domains is studied through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810 S cm -1 , which is not accompanied by a reduction in Seebeck coefficient or a large increase in thermal conductivity. Respectable power factors of 173 µW m -1 K -2 are demonstrated in this model system. The approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Molecular doping-the use of redox-active small molecules as dopants for organic semiconductors-has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl 3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm -1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl 3 , are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counterions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique based on ion exchange, we prepare highly doped films with several counterions of varying size and shape and characterize their carrier density, electrical conductivity, and paracrystalline disorder. In this uniquely large data set composed of several classes of high-mobility conjugated polymers, each doped with at least five different ions, we find electrical conductivity to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parametrized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localization theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disorder-limited nature of charge transport and suggesting new strategies to further improve conductivities.