Dry etch resistance and antireflective performance were studied for a film containing a high amount of carbon (83.4 wt %), which was named the spun-on carbon film. The film was formed by using a carbon cluster precursor synthesized by reductive coupling of a mixture of carbon tetrabromide and phenylbromide. The refractive indices of the spun-on carbon film at the exposure wavelengths of excimer lasers are n = 1.72, k = 0.35 (KrF), n = 1.46, k = 0.67 (ArF), and n = 1.37, k = 0.14 (F-2). A bilayer bottom antireflective coating system composed of upper spun-on glass (SOG) and lower spun-on carbon was evaluated. By optimizing the SOG thickness, the reflectivity is reduced to 0.2% KrF, 3.3% (ArF), and 0.5% (F-2). Remarkable improvement is observed at the KrF and F-2 wavelengths. Resist profiles are obtained without any footing, residue, or standing wave using the KrF and ArF scanning steppers. The etch resistance of the spun-on carbon film is 1.34 times greater than that of the thermally oxidized novolak film (i.e., a conventional underlayer for a trilevel resist process).