CCI Radicals As a Carbon Source for Diamond Thin Film Deposition

We use first-principles quantum mechanical calculations to study diamond thin film growth on the (100) surface using CCI radicals as the carbon source. Our results show that CCI inserts into the surface dimer C–C bonds with a barrier of 10.5 kcal/mol, roughly half of the energy required for traditional CH_2 insertion (22.0 kcal/mol). In addition to this, CCI has improved surface mobility (~30.0 kcal/mol barrier, versus 35 kcal/mol for CH_2, along the C–C dimer chain direction), and hydrogen abstraction from the surface is also favored via atomic CI in the vapor phase. These results explain the lower substrate temperatures achieved in crystal diamond growth from the use of chlorinated sources in CVD processes, as opposed to the more traditional CH_4/H_2 derived species. Our results also suggest that further reductions in substrate temperatures are possible from using CCI as the only carbon source.