The mechanisms leading to the development of an atmospheric low temperature plasma along a surface under pulsed conditions is of current interest. In the early plasma phase, high energy photons are a contributing factor to the process of generating electron avalanches resulting in surface flashover. Since only photons in the vacuum ultraviolet (VUV) regime are energetic enough to cause step-ionization or direct ionization of atmospheric gases, an experiment has been set up to enable observations of photons with wavelengths shorter than 200 nm while still allowing observation up to 800 nm. A spectrum simulation software package has been developed to allow for temperature analysis on the developing plasma in the VUV region. Observations below 200 nm revealed a Boltzmann distributed excited state population corresponding to a temperature of 3.1 eV. Time-resolved emission spectroscopy measurements of the entire electrode region during the streamer phase of breakdown demonstrate the presence of molecular nitrogen emission lines from the second positive system. Further photomultiplier tube measurements of the spark phase showed a rapid decrease in intensity of the second positive system compared to that of a representative atomic emission line in the VUV regime. This emission dominates the ultraviolet-visible (UV-VIS) spectrum during the initial phases of breakdown with little detection of other sources of emission during this phase.