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Understanding the opto-electronic properties of semiconducting polymers underexternal strain is essential for their applications in flexibleopto-electronic, light-emitting and photovoltaic devices. While prior studieshave highlighted the impact of static strains applied on a macroscopic lengthscale, assessing the effect of a local transient deformation before structuralrelaxation occurs is challenging due to the required high spatio-temporalresolution.  Here, we employ scanning ultrafast electron microscopy (SUEM) to image thedynamical effect of a photo-induced transient strain in the archetypalsemiconducting polymer poly(3-hexylthiophene) (P3HT). We observe that thephoto-induced SUEM contrast, corresponding to the local change of secondaryelectron emission, exhibits a ring-shaped spatial profile with a rise time of$\sim 300$ ps, beyond which the profile persists in the absence of a spatialdiffusion. We attribute the observation to the electronic structure modulationof P3HT caused by a photo-induced strain field owing to its relatively lowmodulus and strong electron-lattice coupling, as supported by a finite-elementanalysis. Our work provides insights into tailoring opto-electronic propertiesusing transient mechanical deformation in semiconducting polymers, anddemonstrates the versatility of SUEM to study photo-physical processes indiverse materials.

Transient strain induced electronic structure modulation in a semiconducting polymer imaged by scanning ultrafast electron microscopy