Efficient charge generation contributes greatly to the high performance of organic photovoltaic devices. The mechanism of charge separation induced by heterojunction has been widely accepted. However, how and why free charge carriers can generate in homogenous polymer domains remains to be explored. In this work, the extended tight-binding SSH model, combined with the non-adiabatic molecular dynamics simulation, is used to construct the model of a polymer array in an applied electric field and simulate the evolution of an excited state. It is found that under a very weak external electric field 5.0 × 10−3 V/Å, the excited state can evolve directly into spatially separated free charges at the femtosecond scale, and the efficiency is up to 97%. The stacking structure of the polymer array leads to intermolecular electron mutualization and forms intermolecular coupling. This interaction tends to delocalize the excited states in organic semiconductors, competing with the localization caused by electron–phonon coupling. Excitons within the homogenous polymer domains have lower binding energy, less energy dissipation, and ultrafast charge separation. Therefore, the initial excited state can evolve directly into free carriers under a very weak electric field. This finding provides a reasonable explanation for ultrafast charge generation in pure polymer phases and is consistent with the fact that delocalization always coexists with ultrafast charge generation. Moreover, the devices based on homogenous polymer domains are supposed to be stress-sensitive and performance-anisotropic since the above two interactions have contrary effects and work in perpendicular directions. This work is expected to bring inspiration for the design of organic functional materials and devices.
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