A novel pulsed laser deposition (PLD) process with frozen CH 4 and/or CO 2 is developed. Frozen CH 4 and/or CO 2 formed on the graphitic carbon (GC) target at 12 K, then co-ablated with the GC target, using a KrF excimer laser. The present method is effective in enhancing the dissociation of raw materials and suppressing the large splashing particles. The characteristics of the deposited carbon films depend on the target material and on the substrate temperature. Under the proper conditions, the films show the characteristics of diamond-like carbon in the Raman spectrum. According to the high resolution transmission electron microscopy, these films contain nanometer-sized diamond embryos.