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ABSTRACT Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low-cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi-metallic conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X-ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer-based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 97-104 [ABSTRACT FROM AUTHOR]

Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly(3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics. [ABSTRACT FROM AUTHOR]

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline–crystalline/semiconducting–insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself. [ABSTRACT FROM AUTHOR]

A correction to the article "Semi-metallic polymers" that was published online in a previous issue is presented.

Abstract: Optical spacer layers based on titaniumalkoxide precursor solutions were prepared by spin-coating on top of bulk heterojunction layers based on poly-3-hexylthiophene (P3HT) and phenyl-C61-butyric acid methylester (PCBM). Models and experiment have shown that the performance of polymer solar cells can improve upon application of an optical spacer by shifting the maximum of the electrical field vector of the incident light into the active layer. This avoids the so called “dead zone” close to the reflective electrode. We demonstrate a simple linear model that can be used to predict the intensity variations of the electrical field vector of the incident light through a multilayer structure. Central to our study is the thickness of the optical layer and we find that it is critical to control the optical spacer thickness on the actual active layer employed. X-ray reflectometry allows for the simultaneous determination of the active layer thickness and of the optical spacer layer. [Copyright &y& Elsevier]

Spin-coated poly(9,9-di-n-octylfluorene-alt-benzothiacliazole) (F8BT) films of different molecular weights (Mn = 9—255 kg/mol), both in the pristine and annealed state, were studied in an effort to elucidate changes in the polymer packing structure and the effects this structure has on the optoelectronic and charge transport properties of these films. A model based on quantum chemical calculations, wide-angle X-ray scattering, atomic force microscopy, Raman spectroscopy, photoluminescence, and electron mobility measurements was developed to describe the restructuring of the polymer film as a function of polymer chain length and annealing. In pristine high molecular weight films, the polymer chains exhibit a significant torsion angle between the F8 and BT units, and the BI units in neighboring chains are close to one another. Annealing films to sufficiently high transition temperatures allows the polymers to adopt a lower energy configuration in which the BT units in one polymer chain are adjacent to F8 units in a neighboring chain ("alternating structure"), and the torsion angle between F8 and BT units is reduced. This restructuring, dictated by the strong dipole on the BT unit, subsequently affects the efficiencies of interchain electron transfer and exciton migration. Films exhibiting the alternating structure show significantly lower electron mobilities than those of the pristine high molecular weight films, due to a decrease in the efficiency of interchain electron transport in this structure. In addition, interchain exciton migration to low energy weakly emissive states is also reduced for these alternating structure films, as observed in their photoluminescence spectra and efficiencies. [ABSTRACT FROM AUTHOR]

Poly(ethylene oxide) (PEO) thin films of different thicknesses (220, 450, and 1500 nm) and molecular masses (4000, 8000, and 20 000 g/mol) have been fabricated by spin-coating of methanol solutions onto glass substrates. All these samples have been recrystallized from the melt using a directional thermal gradient technique. Millimeter-size domains with crystallites uniformly oriented in the direction of the thermal gradient are observed. Futhermore, the crystallites size and orientation distribution are enhanced (e.g., increases and decreases, respectively) when film thickness is decreased, ultimately leading to a single-crystal-like behavior for 220 nm thick PEO films of mass 8000 g/mol. Interestingly, this fine microstructure is partially retained after melting and subsequent cooling back to ambient temperature for the highest molecular weight polymer allowing, in this particular case, to significantly decrease the distribution of crystal orientation obtained after crystallization using the thermal gradient technique. [ABSTRACT FROM AUTHOR]

Abstract: Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored. The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head-to-tail connected thiophene units. Annealing was found to relax the P3HT films and increase conjugation length and, in turn, increase stability observed as a delayed spectral blueshift caused by photochemical degradation. Crystallinity was found to play a minor role in terms of stability. Oxygen diffusion and light shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push the technology closer to large-scale applications. [Copyright &y& Elsevier]

Abstract: Large area polymer tandem solar cells completely processed using roll-to-roll (R2R) coating and printing techniques are demonstrated. A stable tandem structure was achieved by the use of orthogonal ink solvents for the coating of all layers, including both active layers. Processing solvents included water, alcohols and chlorobenzene. Open-circuit voltages close to the expected sum of sub cell voltages were achieved, while the overall efficiency of the tandem cells was found to be limited by the low yielding back cell, which was processed from water based ink. Many of the challenges associated with upscaling the multilayer tandem cells were identified giving valuable information for future experiments and development. [Copyright &y& Elsevier]

Abstract: By mapping the small-angle X-ray scattering (SAXS) from a looped poly-(para-phenylene terephtalamide) (aramid, PPTA) filament using a synchrotron X-ray microbeam, we investigate the effects of axially compressive and tensile strain on internal fibrillar structures. Unique observations of oscillations in the highly anisotropic SAXS patterns indicate a regular internal structure. Upon increase of the applied compressive strain, a significant decrease in oscillation frequency is observed in the scattering pattern. With an increase in imposed tensile strain an increase in oscillation frequency in the scattering pattern is observed. One model capable of describing the intensity is a model of stacked cylinders. These cylinders could be part of the fibrillar structure present in the PPTA fibres, which consist of cylinder- to tape-like objects, the presence of which is supported by SEM images. One hypothetical physical interpretation presented here for the appearance of a regular internal structure is the occurrence of fibrillar separation in regions undergoing axially compressive strain, and the appearance of strain relief/slip planes between packs of fibrils in regions undergoing tensile strain. Compaction of these packs upon increase of tensile strain could increase the repetition distance in the structure as multiple packs combine to form a single pack. [Copyright &y& Elsevier]