Towards n-type conductivity in hexagonal boron nitride

Asymmetric transport characteristic in n- and p-type conductivity has long been a fundamental difficulty in wide bandgap semiconductors. Hexagonal boron nitride (h-BN) can achieve p-type conduction, however, the n-type conductivity still remains unavailable. Here, we demonstrate a concept of orbital split induced level engineering through sacrificial impurity coupling and the realization of efficient n-type transport in 2D h-BN monolayer. We find that the O 2p_z orbital has both symmetry and energy matching to the Ge 4p_z orbital, which promises a strong coupling. The introduction of side-by-side O to Ge donor can effectively push up the donor level by the formation of another sacrificial deep level. We discover that a Ge-O₂ trimer brings the extremely shallow donor level and very low ionization energy. By low-pressure chemical vapor deposition method, we obtain the in-situ Ge-O doping in h-BN monolayer and successfully achieve both through-plane (~100 nA) and in-plane (~20 nA) n-type conduction. We fabricate a vertically-stacked n-hBN/p-GaN heterojunction and show distinct rectification characteristics. The sacrificial impurity coupling method provides a highly viable route to overcome the n-type limitation of h-BN and paves the way for the future 2D optoelectronic devices.