Effect of hydrogen on the unintentional doping of 4H silicon carbide

High-purity semi-insulating (HPSI) 4H silicon carbide (4H-SiC) single crystals are critical semiconductor materials for fabricating GaN-based high-frequency devices. One of the major challenges for the growth of HPSI 4H-SiC single crystals is the unintentional doping of nitrogen (N) and boron (B). The addition of hydrogen has been supposed to mitigate unintentional doping. However, the underlying mechanism has not been well understood. In this work, the role of hydrogen in the growth of HPSI 4H-SiC single crystals is investigated by first-principles formation-energy calculations. We find that the addition of hydrogen significantly mitigates N doping while hardly affecting B doping. Once hydrogen is added, hydrogen may adsorb at the growing surface of 4H-SiC, leading to surface passivation. Since N can react with hydrogen to form stable NH3 (g), the chemical potential of N is reduced, so that the formation energy of N in 4H-SiC increases. Hence, the critical partial pressure of nitrogen required for the growth of HPSI 4H-SiC single crystals increases by two orders of magnitude. Moreover, we reveal that the adjustment of relative B and N doping concentrations has a substantial impact on the Fermi energy of HPSI 4H-SiC. When the doping concentration of N is higher than that of B, N interacts with carbon vacancies (VC) to pin the Fermi energy at Z1/2. When the doping concentration of B is higher than that of N, the Fermi energy is pinned at EH6/7. This explains that the resistivity of unintentionally doped HPSI 4H-SiC may vary.