Probing Electronic Band Structures of Dielectric Polymers via Pre‐Breakdown Conduction

Abstract The electronic band structure, especially the defect states at the conduction band tail, dominates electron transport and electrical degradation of a dielectric material under an extremely high electric field. However, the electronic band structure in a dielectric is barely well studied due to experimental challenges in detecting the electrical conduction to an extremely high electric field, i.e., prebreakdown. In this work, the electronic band structure of polymer dielectric films is probed through an in situ prebreakdown conduction measurement method in conjunction with a space‐charge‐limited‐current spectroscopic analysis. An exponential distribution of defect states at the conduction band tail with varying trap levels is observed in accordance with the specific morphological disorder in the polymer dielectric, and the experimental defect states show also a favorable agreement with the calculated density of states from the density functional theory. The methodology demonstrated in this work bridges the molecule‐structure‐determined electronic band structure and the macro electrical conduction behavior with a highly improved understanding of material properties that control the electrical breakdown, and paves a way for guiding the modification of existing material and the exploration of novel materials for high electric field applications.