Competition between deformability and charge transport in semiconducting polymers for flexible and stretchable electronics

The primary goal of the field concerned with organic semiconductors is to produce devices with performance approaching that of silicon electronics, but with the deformability - flexibility and stretchability - of conventional plastics. However, an inherent competition between deformability and charge transport has long been observed in these materials, and achieving the extreme (or even moderate) deformability implied by the word "plastic" concurrently with high charge transport may be elusive. This competition arises because the properties needed for high carrier mobilities - e.g., rigid chains in π-conjugated polymers and high degrees of crystallinity in the solid state - are antithetical to deformability. On the device scale, this competition can lead to low-performance yet mechanically robust devices, or high-performance devices that fail catastrophically (e.g., cracking, cohesive failure, and delamination) under strain. There are, however, some observations that contradict the notion of the mutual exclusivity of electronic and mechanical performances. These observations suggest that this problem may not be a fundamental trade-off, but rather an inconvenience that may be negotiated by a logical selection of materials and processing conditions. For example, the selection of the poly(3-alkylthiophene) with a critical side-chain length - poly(3-heptylthiophene) (n = 7) - marries the high deformability of poly(3-octylthiophene) (n = 8) with the high electronic performance (as manifested in photovoltaic efficiency) of poly(3-hexylthiophene) (n = 6). This review explores the relationship between deformability and charge transport in organic semiconductors. The principal conclusions are that reducing the competition between these two parameters is in fact possible, with two demonstrated routes being: (1) incorporation of softer, insulating material into a stiffer, semiconducting material and (2) increasing disorder in a highly ordered film, but not enough to disrupt charge transport pathways. The aim of this review is to provide a bridge between the fields interested in electronic properties and mechanical properties of conjugated polymers. We provide a high-level introduction to some of the important electronic and mechanical properties and measurement techniques for organic electronic devices, demonstrate an apparent competition between good electronic performance and mechanical deformability, and highlight potential strategies for overcoming this undesirable competition. A marriage of these two fields would allow for rational design of materials for applications requiring large-area, low-cost, printable devices that are ultra-flexible or stretchable, such as organic photovoltaic devices and wearable, conformable, or implantable sensors.