Thermoelectric plastics are a class of polymer-based materials that combine the ability to directly convert heat to electricity, and vice versa, with ease of processing.

No abstract

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers.

We report a record thermoelectric power factor of up to 160 μW m –1 K –2 for the conjugated polymer poly(3-hexylthiophene) (P3HT). This result is achieved through the combination of high-temperature rubbing of thin films together with the use of a large molybdenum dithiolene p-dopant with a high electron affinity. Comparison of the UV–vis–NIR spectra of the chemically doped samples to electrochemically oxidized material reveals an oxidation level of 10%, i.e., one polaron for every 10 repeat units. The high power factor arises due to an increase in the charge-carrier mobility and hence electrical conductivity along the rubbing direction. We conclude that P3HT, with its facile synthesis and outstanding processability, should not be ruled out as a potential thermoelectric material.

The thermoelectric power factor of a broad range of organic semiconductors scales with their electrical conductivity according to a widely obeyed power law, and therefore, strategies that permit this empirical trend to be surpassed are highly sought after. Here, tensile drawing of the conjugated polymer poly(3-hexylthiophene) (P3HT) is employed to create free-standing films with a high degree of uniaxial alignment. Along the direction of orientation, sequential doping with a molybdenum tris(dithiolene) complex leads to a 5-fold enhancement of the power factor beyond the predicted value, reaching up to 16 μW m–1 K–2 for a conductivity of about 13 S cm–1. Neither stretching nor doping affect the glass transition temperature of P3HT, giving rise to robust free-standing materials that are of interest for the design of flexible thermoelectric devices.

Doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with the p-dopant 2, 3,5,7,8, is a widely used model system for organic thermoelectrics.We here study how the crystalline order influences the Seebeck coefficient of P3HT films doped with F4TCNQ from the vapour phase, which leads to a similar number of F4TCNQ anions and hence (bound + mobile) charge carriers of about 2 Â 10 À4 mol cm À3. We find that the Seebeck coefficient first slightly increases with the degree of order, but then again decreases for the most crystalline P3HT films. We assign this behaviour to the introduction of new states in the bandgap due to planarisation of polymer chains, and an increase in the number of mobile charge carriers, respectively. Overall, the Seebeck coefficient varies between about 40 to 60 mV K À1. In contrast, the electrical conductivity steadily increases with the degree of order, reaching a value of more than 10 S cm À1, which we explain with the pronounced influence of the semi-crystalline nanostructure on the charge-carrier mobility. Overall, the thermoelectric power factor of F4TCNQ vapour-doped P3HT increases by one order of magnitude, and adopts a value of about 3 mW m À1 K À2 in the case of the highest degree of crystalline order.

The UV-to-IR transitions in p-doped poly(3-hexylthiophene) (P3HT) with alkyl side chains and polar polythiophene with tetraethylene glycol side chains are studied experimentally by means of the absorption spectroscopy and computationally using density functional theory (DFT) and tight-binding DFT. The evolution of electronic structure is calculated as the doping level is varied, while the roles of dopant ions, chain twisting, and π–π stacking are also considered, each of these having the effect of broadening the absorption peaks while not significantly changing their positions. The calculated spectra are found to be in good agreement with experimental spectra obtained for the polymers doped with a molybdenum dithiolene complex. As in other DFT studies of doped conjugated polymers, the electronic structure and assignment of optical transitions that emerge are qualitatively different from those obtained through earlier “traditional” approaches. In particular, the two prominent bands seen for the p-doped materials are present for both polarons and bipolarons/polaron pairs. The lowest energy of these transitions is due to excitation from the valence band to a spin-resolved orbitals located in the gap between the bands. The higher-energy band is a superposition of excitation from the valence band to a spin-resolved orbitals in the gap and an excitation between bands.

The insulation of state-of-the-art extruded highvoltage direct-current (HVDC) power cables is composed of cross-linked low-density polyethylene. Driven by the search for sustainable energy solutions, concepts that improve the ability to withstand high electrical fields and, ultimately, the power transmission efficiency are in high demand. The performance of a HVDC insulation material is limited by its residual electrical conductivity. Here, we demonstrate that the addition of small amounts of high-density polyethylene (HDPE) to a low-density polyethylene (LDPE) resin results in a drastic reduction in DC conductivity. An HDPE content as low as 1 wt % is found to introduce a small population of thicker crystalline lamellae, which are finely distributed throughout the material. The change in nanostructure correlates with a decrease in DC conductivity by approximately 1 order of magnitude to about 10 −15 S m −1 at high electric fields of 30 and 40 kV mm −1 and elevated temperature of 70 °C. This work opens up an alternative design concept for the insulation of HVDC power cables.