In the context of nitrogen-rich amorphous carbon thin films ultrafast pulsed laser deposition from graphite targets in inert nitrogen or nitrogen plasma ambient, this study assesses the correlation between the ablation plume composition and dynamics and the thin films contents and structures. The use of both optical emission spectroscopy and spectrally resolved 2D imaging, coupled with intensified CCD temporal resolution, allows to precisely follow such species of the plume as CN and C-2 molecules, from their apparition to their deposition on the substrate. The results show that carbon-nitrogen bonding arises at the early time of expansion with little changes in quantity thereafter. The key role of the DC-bias is in lowering the molecular weight of the ambient gas, thus easing molecules way toward the target and interfering with the chemical reaction for CN generation. Depending on the ambient pressure, these processes will have drastically different effects on the thin films properties and contents. This work thus explains the origin of high nitrogen contents in a-C:N thin films obtained using DC-bias, and proposes an easy in situ optical observation-based way to predict and look for the best conditions to maximize those contents in future work.