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Semiconducting polymers have the potential to be used in thermoelectric devices that are lightweight, flexible, and fabricated using solution processing. Because of the structural and energetic disorder of these polymers, the relationship between their structure and thermoelectric properties is complex. We review how interrelated processing routes and doping methods affect the thermoelectric properties of polymers. The studies highlighted here have led to correlations between thermopower and electrical conductivity that can be described by theories under investigation. With greater understanding of the materials properties behind their performance, semiconducting polymers can be used in future power generation or cooling devices. 

Since doped polymers require a charge‐neutralizing counter‐ion to maintain charge neutrality, tailored and high degrees of doping in organic semiconductors requires an understanding of the coupling between ionic and electronic carrier motion. A method of counter‐ion exchange is utilized using the polymeric semiconductor poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] ‐C₁₄to deconvolute the effects of ionic/polaronic interactions with the electrical properties of doped semiconducting polymers. In particular, exchanging the counter‐ions of the dopant nitrosonium hexafluorophosphate enables investigation into the role of counter‐ion size from 5.2 to 8.2 Å in diameter. The orientational order of the polymeric crystallites is not affected with this exchange process while effectively modifying the counter‐ion distance to the charge carrier. Doped films have electrical conductivities of 320 S cm⁻¹and are not sensitive to an increased ion‐polaron distance. It is posited that other factors dominate the electrical properties at a device scale, such as the morphology and presence of domain boundaries. Interestingly, the temperature stability of the doped film can be drastically improved with the use of counter‐ions containing less labile bonds. This platform serves as a unique way to retain the morphology of polymeric thin films while studying charge interactions at the local scale.

 

The heterogeneous microstructure of semicrystalline polymers complicates the relationship between their electrical conductivity and carrier concentration. Charge transport models typically describe conductivity with an assumption of uniform doping throughout the material. Here, the evolution in morphology and optoelectronic properties of poly(3‐hexylthiophene) (P3HT) is reported as a function of carrier concentration in an organic electrochemical transistor using a polymeric ionic liquid (PIL) as the gate insulator.Operandograzing incidence X‐ray scattering reveals that negatively charged ions from the dielectric first infiltrate the amorphous regions of the semiconductor, and then penetrate the crystalline regions at a critical carrier density of 4 × 10²⁰cm⁻³. Upon infiltration, the crystallites expand by 12% in the alkyl stacking direction and compress by 4% in the π–π stacking direction. The change in crystal structure of P3HT correlates with a sharply increasing effective carrier mobility. UV–visible spectroscopy reveals that holes induced in P3HT first reside in the crystalline regions of the polymer, which verifies that a charge carrier need not be in the same physical domain as its associated counterion. The dopant‐induced morphological changes of P3HT rationalize the dependence of mobility on carrier concentration, suggesting a phase transition of crystalline regions at high carrier concentration.