Mechanism Study of Molecular Trap in All‐Organic Polystyrene‐Based Dielectric Composite

Abstract It is a huge challenge to explore how charge traps affect the electric breakdown of polymer‐based dielectric composites. In this paper, alkane and aromatic molecules with different substituents are investigated according to DFT theoretical method. The combination of strong electron‐withdrawing groups and aromatic rings can establish high electron affinity molecules. 4′‐Nitro‐4‐dimethylaminoazobenzene (NAABZ) with a vertical electron affinity of 1.39 eV and a dipole moment of 10.15 D is introduced into polystyrene (PSt) to analyze the influence of charge traps on electric properties. Marcus charge transfer theory is applied to calculate the charge transfer rate between PSt and NAABZ. The nature of charge traps is elaborated from a dynamic perspective. The enhanced breakdown mechanism of polymers‐based composites stems from the constraint of carrier mobility caused by the change in transfer rate. But the electrophile nature of high electron affinity filler can decrease the potential barriers at the metal–polymer interface. Simultaneously, the relationship between the electron affinity of fillers and the breakdown strength of polymer‐based composites is nonlinear because of the presence of the inversion region. Based on the deep understanding of the molecular trap, this work provides the theoretical calculation for the design and development of high‐performance polymer dielectrics.