Fatigue in organic semiconductors: Spectroscopic evolution of microstructure due to cyclic loading in poly(3-heptylthiophene)

• This paper describes the effect of cyclic stretching on a semiconducting polymer.
• The polymer used is the highly stretchable P3HpT.
• Films are strained up to 10,000 times and measured by UV–vis.
• A reduction in aggregation is observed when strained beyond the yield point.
• A reduction in tensile modulus is inferred from a decrease in buckling wavelength.

Organic electronic materials have many characteristics that make them attractive for applications in which mechanical deformability—i.e., flexibility and stretchability—are required. While deformation often degrades the performance of these devices, very little is known about the effects of cyclic loading—i.e., mechanical fatigue—on the microstructure and mechanical properties of the active materials. This paper examines the evolution of microstructure, stiffness, and ductility of thin films of poly(3-heptylthiophene) (P3HpT) as the film undergoes cyclic straining using ultraviolet-visible (UV–vis) spectroscopy and film-on-elastomer techniques. Thin films of P3HpT are cyclically stretched by 5, 10, or 25 percent (i.e., below, at, and above the yield point—the point at which the polymer plastically deforms with strain) up to 10000 cycles. UV–vis absorption spectroscopy is taken in intervals and the weakly interacting H-aggregate model is used to determine the aggregate quantity (from the vibronic progression) and quality (from the exciton bandwidth) in the films. Films cyclically strained at 5 and 10 percent (below and at the yield point) do not undergo significant reduction in the aggregated fraction of polymer chains, while films strained to 25% (above the yield point) undergo a reduction in aggregated fraction of over 10% by the 2000th cycle. At 25% strain, a significant reduction in the buckling wavelength from 3.4 ± 0.4 μm to 2.4 ± 0.3 μm is observed within the first 100 strain cycles suggesting a significant reduction in the stiffness and resilience of the films. A significant decrease in ductility is observed in films cyclically strained, and the effect is found to increase with increasing levels of strain. These results suggest that materials cyclically strained below their yield point will retain a microstructure that is their most electronically favorable, and that the mechanical properties of materials strained above their yield point will evolve significantly under repeated deformation. This information can be used to inform design where accommodation of repetitive strain is required, such as outdoor, portable, and wearable devices.

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