We investigate single domain β-SiC(100) thin film surfaces epitaxially grown on a vicinal (4°) Si(100) surface by atom-resolved (filled and empty states) scanning tunneling microscopy (STM). Contrary to previous beliefs, we observe high quality surfaces having a low density of defects. The β-SiC(100)-(3×2) surface, which is a Si-rich surface, is achieved by sequences of Si deposition and surface annealings. This results in the growth and coalescence of large Si islands and/or vacancies islands having the 3×2 array. Our results indicate the formation of asymmetric Si-Si dimers all tilted in the same direction and forming rows in a 3×2 arrangement at a 1/3 Si mon/layer coverage.