The electronic properties of epitaxial graphene grown on SiC(0001) are known to be impaired relative to those of freestanding graphene. This is due to the formation of a carbon buffer layer between the graphene layers and the substrate, which causes the graphene layers to become strongly n-doped. Charge neutrality can be achieved by completely passivating the dangling bonds of the clean SiC surface using atomic intercalation. So far, only one element, hydrogen, has been identified as a promising candidate. We show, using first-principles density functional calculations, how it can also be accomplished via the growth of a thin layer of silicon nitride on the SiC surface. The subsequently grown graphene layers display the electronic properties associated with charge neutral graphene. We show that the surface energy of this structure is considerably lower than that of others with intercalated atomic nitrogen and determine how its stability depends on the N 2 chemical potential. The thermal decomposition of silicon carbide (SiC) is one of the most promising methods to produce high-quality epitaxial graphene on a wafer scale, directly on a semiconducting surface. However, the electronic properties of the resultant graphene have been shown to depend intimately on the chosen SiC surface. When graphene is grown on the Si-rich SiC(0001) surface, the first carbon layer is covalently bonded to the surface Si atoms, with only subsequent layers displaying the characteristic electronic features of graphene. Furthermore, these graphene layers are heavily doped, due to charge transfer from the surface, and have a considerably reduced electron mobility compared to freestanding graphene [1][2][3].Several attempts have been made to electronically decouple the so-called carbon buffer layer or "zeroth layer" graphene (0LG) from the substrate and thereby reduce the intrinsic electron doping. A promising technique to do so is by intercalating atoms or molecules between the 0LG and the SiC substrate [4][5][6][7][8]. Hydrogen intercalation has been shown to reproducibly decouple the buffer layer from the substrate [9], increasing the carrier mobility to more than 11000 cm 2 V −1 s −1 at 0.3 K [10]. However, the resulting quasifreestanding monolayer graphene is slightly p-doped [11] due to the intrinsic spontaneous polarization of hexagonal SiC [12,13].Attaining charge neutrality is vital to achieve the high electron mobilities associated with freestanding or suspended graphene [14]. The intercalation of highly electronegative atoms, such as N, O, and F, could be expected to reduce or even eliminate the intrinsic n-type doping of graphene. However, F intercalation results in strong p-doping [15], while O intercalation is difficult to control [16][17][18]. The effect of nitrogen intercalation on the electronic structure of graphene on SiC has only recently been addressed. Wang et al. [19] showed that, after thermal treating with NH 3 , dissociated N species intercalate between the 0LG and the substrate, weakening the interaction between t...