In this paper, the characteristics of a nanosecond spark discharge with a pin–pin electrode configuration have been systematically studied. Both a streak camera with high temporal resolution and an intensified charge-coupled device (ICCD) camera are employed together to investigate the breakdown and evolution process of the discharge. The formation of initial breakdown and mode transition from streamer to spark in the electrode gap are clearly observed on the time scale of several nanoseconds with a temporal resolution of 100 ps. In addition, the time-resolved spectra technology is also used to analyze the generation and quenching mechanisms of reactive species, the electron density, and the electron temperature. The results show that there is a 1.25 ns initial discharge breakdown and that a bright cathode spot exists before the transformation from streamer to spark channel. After a faster cathode filament and a slower anode filament propagate and merge at the electrode gap, the spark discharge phase begins. The generation processes of different reactive species depend on the discharge phase to a great extent. The N2* is first generated during the streamer phase while the O*, N*, and N+ are mainly generated under the spark phase, in which the electron temperature calculated by Boltzmann plots is 2.74 eV, and the electron density determined from the Stark broadening of O lines is on the order of 1016 cm−3.
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