Atomistic mechanisms of codoping-induced p- to n-type conversion in nitrogen-doped graphene

It was recently shown that nitrogen-doped graphene (NG) can exhibit both p- and n-type characters depending on the C-N bonding nature, which represents a significant bottleneck for the development of graphene-based electronics. Based on first-principles calculations, we herein scrutinize the correlations between the atomic and electronic structures of NG and particularly explore the feasibility of converting p-type NG with pyridinic, pyrrolic, and nitrilic N atoms into n- or bipolar type by introducing an additional dopant atom. Of the nine candidates B, C, O, F, Al, Si, P, S, and Cl, we find that B-, Al-, and P-codoping can anneal even relatively large vacancy defects in p-type NG. It will be also shown that, while the NG with pyridinic N can be converted into the n-type via codoping, only a bipolar type conversion can be achieved for the NG with nitrilic or pyrrolic N. The amount of work function reduction was up to 0.64 eV for the pyridinic N next to a monovacancy. The atomistic origin of such diverse type changes is analyzed based on Mulliken and crystal orbital Hamiltonian populations, which provide us with a framework to connect the local bonding chemistry with the macroscopic electronic structure in doped and/or defective graphene. Moreover, we demonstrate that the proposed codoping scheme can recover the excellent charge transport properties of pristine graphene. Both the electronic type conversion and conductance recovery in codoped NG should have significant implications for the electronic and energy device applications.