Acceptor and donor impurity levels in hexagonal-diamond silicon

Abstract: Recent advances in the characterization of hexagonal-diamond silicon (2H-Si) have shown that this material possesses remarkably different structural, electronic, and optical properties as compared to the common cubic-diamond (3C) polytype. Interestingly, despite the wide range of physical properties analyzed, to date no study has investigated impurity energy levels in 2H-Si. Here, we present results of ab initio DFT simulations to describe the effect of p- and n-type substitutional doping on the structural and electronic properties of hexagonal-diamond Si (2H-Si). We first provide a detailed analysis of how a given impurity can assume a different local symmetry depending on the host crystal phase. Then, by studying neutral and charged dopants, we carefully estimate donors and acceptors transition energy levels in 2H-Si and compare them with the cubic-diamond (3C) case. In the case of acceptors, the formation energy is always lower in 2H-Si and is associated with a shallower charge transition level with respect to 3C-Si. On the other hand, donors prefer the cubic phase and have transition energies smaller with respect to 2H-Si. Finally, by employing a simple model based on the 2H/3C band offset diagram, we prove the physical validity of our findings and we show how holes can be used to stabilize the 2H-Si phase. Overall, the described doping properties represent a robust starting point for further theoretical and experimental investigations.