Field-Induced Carrier Localization Transition in Dielectric Polymers

Organic polymers offer many advantages as dielectric materials over their inorganic counterparts because of high flexibility and cost-effective processing, but their application is severely limited by breakdown in the presence of high electric fields. Dielectric breakdown is commonly understood as the result of avalanche processes such as carrier multiplication and defect generation that are triggered by field-accelerated hot carriers (electrons or holes). In stark contrast to inorganic dielectric materials, however, there remains no mechanistic understanding to enable quantitative prediction of the breakdown field in polymers. Here, we perform systematic study of different electric fields on hot carrier dynamics and resulting chemical damage in a slab of archetypal polymer, polyethylene, using nonadiabatic quantum molecular dynamics simulations. We found that high electric fields induce localized electronic states at the slab surface, with a critical transition occurring near the experimentally reported intrinsic breakdown field. This transition in turn facilitates strong polaronic coupling between charge carriers and atoms, which is manifested by severe damping of the time evolution of localized states and the presence of C-H vibrational resonance in the hot-carrier motion leading to rapid carbon-carbon bond breaking on the surface. Such polaronic localization transition may provide a critically missing prediction method for computationally screening dielectric polymers with high breakdown fields.