Theoretical study of edge states in BC2N nanoribbons with zigzag edges
© Harigaya and Kaneko; licensee Springer. 2013
Received: 24 May 2013
Accepted: 23 July 2013
Published: 31 July 2013
In this paper, electronic properties of BC2N nanoribbons with zigzag edges are studied theoretically using a tight binding model and the first-principles calculations based on the density functional theories. The zigzag BC2N nanoribbons have the flat bands when the atoms are arranged as B-C-N-C along the zigzag lines. In this arrangement, the effect of charge transfer is averaged since B and N atoms are doped in same sublattice sites. This effect is important for not only the formation of flat bands but also for the validity of the tight binding model for such system.
Graphene nanoribbons are finite-width graphene sheets, which are the one of the famous examples of nanocarbon materials[1, 2]. The electronic properties of graphene nanoribbons strongly depend on the edge structures. Graphene nanoribbons with zigzag edges have the so-called flat bands at the Fermi level[1, 2]. The states corresponding the flat bands are localized at the zigzag edges, i.e., the namely edge states[1, 2]. In the honeycomb lattice, there are two inequivalent sites, A and B sublattices. For the formation of edge states, this sublattice structure plays decisive role[1, 2].
On the other hand, boron-carbon-nitiride (BCN) materials, such as BCN nanotubes and graphite-like BCN, were synthesized by many groups[3–7]. Quite recently, BCN sheets with BN and graphene domains were synthesized by Ci et al.. Furthermore, a controllability of domain shapes was reported. Fabrication of BCN nanoribbons was expected[10–14]. Therefore, such systems attract considerable interest for application for future electric and optoelectric materials.
Graphite-like BC2N sheet is one of the example of BCN, which was synthesized using chemical vapor depositions of boron trichloride, BCl3, and acetronitrile, CH3CN[15, 16]. The stabilities and electronic properties of BC2N sheets were investigated by several authors[17–19]. The electronic and magnetic properties of nanoribbons made with BC2N sheets were also investigated by several authors[20–24]. The magnetism in BC2N nanoribbons is predicted[20, 21, 23, 24]. Xu et al. reported the presence of linear dispersion when atoms are arranged as C-B-N-C in the transverse direction.
Previously, the authors reported that the flat bands appear in zigzag BC2N nanoribbons where the atoms are arranged as B-C-N-C along the zigzag lines using a tight binding (TB) model. The TB approximation is an efficient method to describe the electronic properties compared with the density functional theories (DFT). In the TB approximation, however, the effect of the charge transfer is absent, resulting in the failure of TB model for B- and N-doped nanocarbon system. The purpose of the paper was to investigate the effect of charge transfer in BC2N nanoribbons theoretically.
In this paper, we investigate the electronic properties of BC2N nanoribbons with zigzag edges using the TB model and the first-principles calculations based on DFT. The zigzag BC2N nanoribbons have the flat bands and edge states when atoms are arranged as B-C-N-C along the zigzag lines. The validity of TB approximation is discussed.
We performed the first-principles calculations based on DFT using the local density approximation (LDA) and the projector augmented wave method implemented in VASP code. The cell size in the one-dimensional direction was measured by the lattice constant of BC2N sheet, a = 4.976 Å, and the ribbons were isolated by vacuum region with about 12 Å in thickness. The outermost atoms are terminated by single H atoms. The geometry was fully optimized when the maximum forces fell down below 10−3 eV/Å. The cutoff energy of the plane wave basis set was chosen to be 400 eV, and the k-point sampling was chosen to be 12 in the one-dimensional direction. Although we found the finite spin polarization in BC2N nanoribbons, we restricted spin unpolarized calculations. The results of spin-polarized band structures will be reported in future publications elsewhere together with other models of BC2N nanoribbons.
where E i is an energy of π electron at the site i; and c i are the creation and annihilation operators of electrons at the lattice site i, respectively; 〈i,j〉 stands for summation over the adjacent atoms; and ti,j is the hopping integral of π electrons from j th atom to i th atom. E i are the site energies, EB, E C , and E N , at the B, C, and N sites, respectively. Following the work of Yoshioka et al., we shall assume that the hopping integrals are constant regardless of the atoms, i.e., ti,j ≡ t, and E N = −EB and E C = 0. For the numerical calculations, we shall choose EB/t = 0.7, 1.0 and 1.3[24, 25].
Results and discussion
Calculated formation energies of BC 2 N nanoribbons for N = 8
where, EGr, EBN, and are total energies of BC2N nanoribbons, graphene, boron nitride sheet, and hydrogen molecules, respectively. The model C and D BC2N nanoribbons are stable compared with models A and B due to the large number of C-C and B-N bonds. Previously, we considered the BCN nanoribbons where the outermost C atoms were replaced with B and N atoms. In these nanoribbons, H atoms tend to be adsorbed at B atoms. For the model C and D BC2N nanoribbons, however, a termination of the outermost B atoms is not energetically favorable compared with a termination of the outermost N atoms. Similar behavior can be found for the zigzag and armchair BN nanoribbons. The outermost B (N) atoms are connected with single N (B) atoms for the model C and D BC2N nanoribbons, while the outermost B and N atoms are connected with only C atoms for the previous models’ nanoribbons. Such difference between atomic arrangement should lead different tendency on the enegetics.
The band structures of the model B nanoribbons also show similar dependence. It should be emphasized that the atoms are arrange as B-C-N-C along the zigzag lines in the model A and B nanoribbons. As reported before, we can expect that the bands around the Fermi level would degenerate with increasing of N.
In the model C nanoribbons, the band structure within DFT shows the flat bands around the Fermi level, but they are not degenerate. It should be noted that electron-hole symmetry is broken in the model C nanoribbons and atoms are not arranged as B-C-N-C along the zigzag lines. On the other hand, the band structures within TB model do not have the flat bands at E = 0. While such prominent bands are not described well, we can see the correspondence between the result within DFT and that of TB model for EB/t = 1.3. Due to the relation E N = −EB, the positive energy states of the model C becomes negative in model D, vice versa. Therefore, we can find similar effect to model C in the band structures, i.e., the band structure within TB model of EB/t = 1.3 is similar to that of DFT except around the Fermi level.
We tried to describe the band structure of models C and D using TB model by introducing the extra site energies at the edges. In this study, we added EB/2 at the outermost N atoms for the model C nanoribbon and −EB/2 at the outermost B atoms for the model D nanoribbon, because such prescription found to show the relatively good performance. The results for EB/t = 1.3 are shown in Figure2c(image iv), d(image iv) by the blue dotted lines. The energy bands around E = 0 in the vicinity of the Γ are shifted upward (downward) by the prescriptions for model C (D), showing that the band structures became much similar to those within DFT.
Calculated band structures are presented in Figure4b. As shown in Figure4b(image ii), the band structure within TB model for EB/t = 1.3 have a finite bandgap which does not decrease with increasing of the ribbon width. On the other hand, the band structure within DFT has a tiny direct bandgap of 0.12 eV at the X point. The decrease of band gap was reported by Lu et al.. It should be noted that we confirmed that the band structure was not improved even if we introduce the site energies at the outermost atoms. Therefore, the arrangement of B-C-N-C along zigzag lines plays a decisive role for the applicability of TB model for BC2N nanoribbons.
Therefore, the energy bands concentrate on these values at k = ±π except edge sites, suggesting that the introduction of the edge site energy is not sufficient to improve the description of electronic properties of BC2N nanoribbons within TB model.
In the model F nanoribbons, the degeneracy at k = π within TB model is lifted in the band structure within DFT. The BC2N nanoribbons where atoms are arranged as C-B-N-C in the transverse direction do not have such degeneracies. These results indicate that the effect of charge transfer penetrates into interior of nanoribbons, resulting in a formation of transverse gradient of electrostatic potential. In the model C and D nanoribbons, on the other hand, the edge dominant states could not be described within TB calculations. For these nanoribbons, the direction of B-N bonds should play important role. In the BC2N sheet shown in Figure1, the direction of BN dimers is arranged alternately. Then, the formation of transverse gradient of electrostatic potential in the nanoribbons is suppressed due to alternate arrangement of BN dimers in slant angle.
Previously, the authors reported that the arrangement of B-C-N-C along zigzag lines plays a decisive role for the formation of the edge states in zigzag BC2Nnanoribbons. This arrangement has other meaning. Within the TB approximation, effect of charge transfer is not described. On the other hand, B (N) atoms act as acceptors (donors) in graphene. Since B and N atoms occupy the same sublattice sites, the effect of charge transfer is canceled when the atoms are arranged as B-C-N-C along zigzag lines. Therefore, TB model is applicable for the zigzag BC2N nanoribbons when the atoms are arranged as B-C-N-C along zigzag lines.
The electronic properties of BC2N nanoribbons with zigzag edges have been studied theoretically using the tight binding model and the first-principles calculations. When atoms are arranged as B-C-N-C along the zigzag lines, the zigzag BC2N nanoribbons have the flat bands. Then, the tight binding model can become applicable for these systems. In this arrangement, the charge transfer is averaged effectively since B and N atoms are substituted in same sublattice sites, and such effect plays an important role for the formation of the edge states. For the tight binding model, the ratio of the site energies of B atom to the hopping integral is larger than unity. We tried to describe the band structure of BC2N nanoribbons where the atoms are not arranged as B-C-N-C along the zigzag lines using the tight binding model by introducing the extra site energies at the outermost atoms, but such method does not work for some BC2N nanoribbons. Therefore, study on the electronic properties of BC2N nanoribbons should be done within the first-principles calculations.
The authors acknowledge H. Imamura, Y. Shimoi, H. Arai, H. Tsukahara, K. Wakabayashi, and S. Dutta for valuable discussions. This research was supported by the International Joint Work Program of Daeduck Innopolis under the Ministry of Knowledge Economy (MKE) of the Korean Government.
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