The operating safety of spacecraft in space environments is closely related to the surface discharging phenomenon of dielectrics such as polyimide (PI) film in solar arrays; moreover, carrier traps in the dielectric can affect its insulation performance. Therefore, to improve the vacuum surface flashover characteristics of PI film by nano modification and reveal the effect of trap distribution on the flashover of PI composite film, first, the original PI and nano-ZnO/PI composite films with different additive amounts (0.5, 1, 2, and 3 wt.%) were prepared by in situ polymerization and their performance was evaluated by the physicochemical properties characterized by methods such as thermogravimetric analysis; second, the surface traps of the original and nanocomposite films were measured and calculated by surface potential decay method, and the carrier mobility was also obtained; finally, the vacuum direct current (DC) surface flashover characteristics and bulk resistivity of all the film samples were measured and analyzed. The experiment results showed that with the increase in the amount of nano-ZnO, both the shallow and deep trap density increased significantly, while the trap energy varied slightly, and the surface flashover voltage also increased obviously. Based on the multi-core model, the increases in the shallow and deep trap density after the introduction of nano-ZnO into the PI matrix was analyzed from the microscopic perspective of the interface. Based on the comparative analysis of the trap distribution and surface flashover voltage characteristics, a bilayer model of vacuum DC surface flashover development was proposed. In the bilayer model, deep traps and shallow traps play a dominant role in the vacuum–solid interface and the inner surface of the dielectric, respectively, and increasing the trap density could effectively inhibit secondary electron multiplication on the surface and accelerate charge dissipation inside the film. Consequently, nano-ZnO can purposefully control the trap distribution, and then improve the flashover characteristics of nano-ZnO/PI composite films, which provides a new approach for improving the spacecraft material safety.
