Pure Hexagonal Diamond with Symmetry-Doping Properties

The difficulties in asymmetrical doping of wide band gap materials, especially for the n-type diamond challenge, hamper their application in electronic devices. Here, we propose doping diamond polytypes with reasonable band structures to solve this problem. Various elements are doped into six diamond polytypes, and their doping behaviors are investigated. The results show that pure hexagonal (2H) diamond has the band gap with a value of 4.42 eV and the smallest carrier effective masses among six calculated diamond polytypes, exhibiting high electron mobility and hole mobility up to 4250 and 5840 cm²·V^-1·s^-1, respectively. Compared to cubic (3C) diamond, the impurity formation energy in 2H-diamond is reduced, which is attributed to its C symmetry. More importantly, 2H-diamond exhibits favorable doping symmetry with a donor level of 0.14 eV for phosphorus and an acceptor level of 0.19 eV for boron, respectively, which originate from smaller effective masses and stronger delocalization at the band edge in 2H-diamond. These ionization energies are smaller than those in 3C-diamond of 0.32 and 0.58 eV, respectively. This reveals that phosphorus and boron in 2H-diamond are more easily excited at room temperature, producing good n- and p-type conductivities. All of these make 2H-diamond a potential candidate for the replacement of 3C-diamond as a wide band gap material theoretically. These provide a way to realize high-quality n-type diamond, giving significant insights into the realization of diamond-based electronic devices. This also supplies a solution for the difficulties in asymmetric doping of other wide band gap materials.