Atomic Structure, Electronic Properties, and Reactivity of In-Plane Heterostructures of Graphene and Hexagonal Boron Nitride

Abstract

We applied density functional theory (DFT) to investigate structural and electronic properties, as well as the reactivity of in-plane heterostructures composed of graphene and hexagonal boron nitride (h-BN). The calculations demonstrate a strong tendency of graphene and h-BN to minimize the number of C−N and C−B bonds and thus to segregate into homogeneous domains. A simple bond model, with parameters obtained from DFT calculations, is used to describe trends in the formation energies of the studied heterostructures. We show that the electronic properties of the BN clusters embedded into graphene qualitatively resemble those of graphene antidot lattices. The calculations also reveal that the h-BN monolayer doped with small graphene clusters is a material with the band gap tunable over an energy range of several electron volts, since the band gap values strongly depend on the size of embedded graphene quantum dots. The reactivity of the graphene/h-BN heterostructures is quantified using H atoms as a probe. We found a strong increase of the H binding energy in the heterostructures, where localized electronic states appear in the vicinity of the Fermi level. The highest value of 2.31 eV, calculated for the ideal zigzag graphene/h-BN interface, is approximately three times larger compared to the H atom binding energy at an infinite graphene sheet.

Microscopic insight into the single step growth of in-plane heterostructures between graphene and hexagonal boron nitride

“…We also show that by varying the deposition conditions very small h-BN/graphene Janus nanodots can be formed with a high yield. Furthermore, the large density of interfaces that can be obtained by this synthesis protocol, provides the ideal material platform for studying the catalytic properties of in-plane heterostructures [16,17,18,56,57], and their defectivity [58].…”

“…The characterization of such systems is very challenging and requires the use of sophisticated techniques that are able to investigate chemical and structural properties at the atomic level. Nonetheless, 2D heterostructures are currently sparking a great deal of interest: theoretical calculations predict that in-plane interfaces should possess novel electronic [10,11,12,13,14,15] and physicochemical properties [16,17,18,19] which can be the stepping stone for developing new devices and atomically thin circuitry [20,21,22,23]. Therefore, it is of great importance to develop strategies for preparing interfaces engineered at the atomic scale and to characterize their unique properties.…”

Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene

“…The formation energy for the different (B, N, and B/N) dopant structures in Table 1 58,62,63 Furthermore, analysis of structures with two or three separated B/N pairs shows a formation energy approximately linear in the number of such pairs. The other structural motifs, such as STM2, have B−N nearest neighbor pairs, but with different organization and shared sites (e.g., the shared B site for STM2 in Figure 3c).…”

Metal-free ferromagnetic metal and intrinsic spin semiconductor: two different kinds of SWCNT functionalized BN nanoribbons

“…[37][38][39] It is known that the dangling bonds of pristine BNNRs are rather active and can be easily passivated. 40,57 Recently, hybrid structures of BNNRs and graphene nanoribbons have also been proposed, [58][59][60][61][62][63][64][65][66] such as the hybrid BN-C nanoribbons, [59][60][61][62][64][65][66] which are considered as graphene nanoribbons embedded in BN nanostructures and vice versa, and show rich electronic and magnetic properties. 11), it turns into a nonmagnetic semiconductor with an indirect wide band gap owing to the largely ionic nature of the N-B bonds.…”