Theory of Doping of Diamond

Electronic applications of diamond require control over native defects as well as the ability to dope it p- and n-type. B is an excellent p-type dopant, but n-type doping has proven very difficult. Diamond films have also been very difficult to anneal, indicating a high activation energy for self-diffusion. We have investigated the properties of native defects and impurities through large-scale band structure and Car-Parrinello calculations. We indeed find that the activation energy for self-diffusion is very high in the intrinsic material, but it decreases by as much as 3 eV in either p- or n-type material. P, Li, and Na are shallow donors, but their solubilities are too low for incorporation into diamond through in-diffusion. It is energetically favorable for B and N to dissolve in diamond, which explains their prevalence in natural diamond. The calculations explain for the first time the reasons for the distortion of atoms around N from the fully tetrahedral site, as well as why N is a deep rather than a shallow donor. We also consider the effects of simultaneous doping with N and B on the thermodynamic equilibrium between diamond and graphite.