In an ongoing effort to investigate plasma plume features yielding high quality diamond-like carbon films, we have applied plasma plume diagnosis and film characterization to examine plume character distinction from KrF laser ablation of both amorphous carbon (a-C) and single crystal graphite (SCG) targets. The advancing plasma plume produced by these structurally different targets are observed to possess quantitatively similar total heavy particle inventory, ionized fraction, and electron thermal content, yet quite different ion kinetic energy, plume profile, C2 formation mechanism, and concentration of complex molecules. Plume electron temperatures are observed to reside in the range 1–3 eV, with those in SCG plumes ∼10%–30% greater than a-C at all spatial positions downstream of the target. For both target cases, we find Te drop off with position away from the target with radiation as the most likely loss mechanism for these noninteracting plumes propagating in vacuum. Electron density is found to be ∼10%–12% lower near the target in SCG than a-C plumes consistent with mass loss inventory measurements, whereas ion fractions are estimated in the range ∼10%–15% for both target cases. All recorded data support the conclusion that the SCG target plasma plume is populated with heavier, more complex molecules than those in a-C which have been shown to be predominantly comprised of C and C+ under vacuum conditions with the addition of C2 at high fill pressure. A significantly smaller profile peaking factor for SCG plumes supports this conclusion. Less energetic and slightly l- ower temperature SCG plume conditions are consistent with reduced peaking and more massive plume species. Plasma plumes from SCG targets exhibit laser energy (El) dependent peaking, again consistent with more complex molecules increasingly disassociated with El increase. The El dependence further suggests the potential for control of particle size distribution and plume profile peaking, though not independently. Consistent with this scenario is the observation of harder films produced from SCG targets at lower El. Micro-Raman results indicate strongly heterogeneous films deposited by SCG target ablation even under vacuum conditions further supporting the case for more complex structures with greater hardness. Energy balance estimates indicate that ion kinetic energy dominates the balance and that SCG ablation liberates about twice the number of 12C atoms from the target per unit El. As well, high pressure background fill indicates lesser plume energy attenuation for SCG plumes, again suggesting the presence of higher mass particles. © 2000 American Institute of Physics.