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The mechano‐electrical properties of poly(3‐hexylthiophene) thin films are investigated as a function of their tie‐chain content. Tie chains play an indispensable role in enabling strain‐induced structural alignment and charge‐transport enhancement in the strain direction. In the absence of sufficient tie chains, the external mechanical force cannot induce any significant polymer backbone alignment locally or crystallite reorientation at the mesoscale. These samples instead undergo brittle fracture on deformation, with cracks forming normal to the direction of strain; charge transport in this direction is hindered as a consequence. This mechanistic insight on strain alignment points to the promise of leveraging tie‐chain fraction as a practical tuning knob for effecting the mechano‐electrical properties in conjugated polymer systems. [ABSTRACT FROM AUTHOR]

The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into poly(3-hexylthiophene-2,5-diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X-ray data suggest that F4TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π-stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6-8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F4TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm2 V−1 s−1 in the most crystalline P3HT samples. Temperature-dependent conductivity measurements show that polaron mobility in SqP-doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature. [ABSTRACT FROM AUTHOR]

Naphthalenediimide (NDI)-based polymers co-polymerized with thienyl units are an interesting class of polymer semiconductors because of their good electron mobilities and unique film microstructure. Despite these properties, understanding how the extension of the thienyl co-monomer affects charge transport properties remains unclear. With this goal in mind, we have synthesized a series of NDI derivatives of the parent poly{[ N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene) (P(NDI2OD-T2)), which exhibited excellent electron mobility. The strategy comprises both the extension of the donor o-conjugation length and the heteroatomic fusion of the thiophene rings. These newly synthesized compounds are characterized experimentally and theoretically vis-à-vis with P(NDI2OD-T2) as the reference. UV-vis data and cyclic-voltammetry are adopted to assess the effect of the donor modification on the frontier energy levels and on the bandgap. Intra-molecular polaronic effects are accounted for by computing the internal reorganization energy with density functional theory (DFT) calculations. Finally electrons and holes transport is experimentally investigated in field-effect transistors (FETs), by measuring current-voltage characteristics at variable temperatures. Overall we have identified a regime where inter-molecular effects, such as the wavefunction overlap and the degree of energetic disorder, induced by the different donor group prevail over polaronic effects and are the leading factors in determining electrons mobility. [ABSTRACT FROM AUTHOR]

Abstract: The problem that conventional time of flight (TOF) mobility measurements are made on much thicker films than typically used in organic optoelectronic devices is investigated by comparing the mobility of thick and thin films of the poly(phenylenevinylene) based copolymer “SuperYellow”. We report for the first time mobility values perpendicular to the substrate for this widely used material and find them to be of the order of 10−6–10−7 cm2/Vs for both spin-coated and drop-cast films. A high photoluminescence quantum yield (PLQY) of 60±5% is measured for both types of films. The results indicate a trade-off between PLQY and charge transport in poly(arylenevinylene)s. The insensitivity of the charge transporting and photophysical properties to the film preparation procedure and thickness is a desirable characteristic that may result from the bulky side groups of “SuperYellow”. [Copyright &y& Elsevier]

Stretchable electronics have increasingly gained interest both in the academic and industrial communities owing to its potential to enable a wide variety of applications, especially wearable and implantable devices for biomedical applications. As the key component for electronic devices, the design of a suitable semiconductor is essential, while the solution processability and structural tunability of polymer semiconductor make it a promising candidate. Along this line, it is important to consider the mechanical properties of polymer semiconductors in the design of flexible and stretchable devices placed on soft and curved surfaces to accommodate the constant movement of the human body. However, achieving high mechanical deformability and high charge transport properties simultaneously in polymer semiconductors remains a major challenge. In this trend article, we survey various approaches in designing intrinsically stretchable conjugated polymers, focusing on structure-property relationships from a molecular perspective, such as molecular weight, regioregularity, backbone and side chain modifications. Understanding the influence of these molecular structure parameters on thin film morphology may provide general guidelines for achieving desired microstructures that allow mechanical deformation without interrupting charge transport. Beyond highlighting recent key work in this field, we will discuss future prospects of stretchable conjugated polymers. [ABSTRACT FROM AUTHOR]