Plasma Characterization of Pulsed-Laser Ablation Process Used for Fullerene-like CNx Thin Film Deposition

An in situ Optical Emission Spectroscopy (OES) characterization was performed on Pulsed-Laser Ablation (PLA) process used for fullerene-like CNx thin film deposition at nitrogen pressures within the 5 – 100 mTorr range. Plumes were generated by ablation of pyrolytic graphite (99.99%) target using a (500 mJ, 7 ns, 1064 nm) Nd: YAG-pulsed laser. The spectra from the plume show, essentially, the presence of the band heads of CN Violet vibrational/rotational BΣXΣ system and the characteristic C2 emission lines, belonging to the Swan AΠg X’3Πu system. These excited CN and C2 molecules were generated by laser ablation and by collisions of the plume with the substrate surface. Their vibrational temperatures were strongly dependent on nitrogen pressure during the deposition process and presented a decrease between 2.64 and 1.23 eV, as pressure increased from 5 to 100 mTorr. Synthesis of fullerene-like structures required high molecular temperatures at the condensation surface. High concentrations of CN radicals in the plasma promoted nitrogen incorporation into the films. The OES plasma characterization allowed for a correlation of the concentration and vibrational temperatures of CN and C2 species present in the plasma with the fullerene-like CNx film composition and bonding, determined by XPS, IR, and Raman spectroscopy.