Diamond-like carbon (DLC) films were deposited utilising plasma enhanced chemical vapour deposition (PECVD) with acetylene precursor, diluted with 0-45% argon. Electron paramagnetic resonance (EPR) measurements show the presence of one paramagnetic centre with no change in spin population over the range of film deposition conditions. However, the EPR linewidth decreases with increasing argon content of the precursor mix, suggesting an enhancement of motional narrowing due to an increase in electron delocalization, related to an increase in the sp2 cluster size. Atomic force microscopy (AFM) measurements indicate that the surface of the DLC is formed of nanoscale asperities of material. With radii of tens of nanometres for films deposited with zero argon, the size of the features increases with the argon dilution of the acetylene. Energy dispersive X-ray analysis and electrical measurements further elucidate the changes in film structure.