Abstract
We investigate the Dirac cone in αgraphdiyne, which is a predicted flat oneatomthick allotrope of carbon using firstprinciples calculations. αgraphdiyne is derived from graphene where two acetylenic linkages (C ≡C) are inserted into the single bonds (CC). Thus, αgraphdiyne possesses a larger lattice constant which subsequently affects its electronic properties. Band structures show that αgraphdiyne exhibits similar Dirac points and cone to graphene. Further, the tightbinding method is used to exploit the linear dispersion in the vicinity of Dirac points. Thanks to the larger lattice constant, αgraphdiyne yields a lower Fermi velocity, which might make itself an ideal material to serve the anomalous integer quantum Hall effect.
Keywords:
αgraphdiyne; Dirac cone; Firstprinciples calculationBackground
Band theory was first used to study the band structure of graphene over half a century
ago [1], and it demonstrated that graphene is a semimetal with unusual linearly dispersing
electronic excitations called Dirac electron. Such linear dispersion is similar to
photons which cannot be described by the Schrödinger equation. In the vicinity of
the Dirac point where two bands touch each other at the Fermi energy level, the Hamiltonian
obeys the twodimensional (2D) Dirac equation [2] as
Recently, it was found that Dirac cones not only occur in the 2D carbon allotropes such as graphene, graphyne, and graphdiyne [4], but also can be detected at interfaces of topological insulators [511]. It is notable that, in 6,6,12graphyne [4], the conduction electrons turn out to be superior to that in graphene in one preferred direction over the other, which is due to the rectangular lattice. This is a major step in searching for new Dirac cone materials. Therefore, it is proper to pursue the Dirac cone material with tunable Fermi velocity, which will be the focus of future researches.
In this letter, we predict a novel flat oneatomthick allotrope of carbon by inserting two acetylenic linkages into the single bonds in graphene. According to the naming method used in [4], we assign it as αgraphdiyne. Up to now, no study has been made on αgraphdiyne both experimentally and theoretically. Thus, theoretical investigation on αgraphdiyne is a must before synthesizing it in experiments. Since αgraphdiyne has a larger lattice constant, it should have potential applications both in quantum tunneling [12] and in anomalous integer quantum Hall effect [13]. In this work, band structures are calculated and a similar Dirac cone to that of graphene is observed. In particular, we introduce a tightbinding model to mimic the hopping energy between the hexagonal vertices, which realizes the linear dispersion of bands near the Dirac points, allowing the Dirac cone to be studied explicitly.
Methods
To simulate the electronic properties, we employ density functional theory with the generalized gradient approximation (GGA) of PerdewBurkeErnzerhof (PBE) [14] for the exchangecorrelation (XC) potential within the projector augmented wave method, as implemented in VASP [15]. The cutoff energy for plane waves is set to be 500 eV. The vacuum space is at least 15 Å, which is large enough to avoid the interaction between periodical images; 15 ×15×1 and 25 ×25×1 are used for the kgrid of geometry optimization and selfconsistent calculation, respectively. During the geometry optimization, all the atoms in the unit cell were allowed to relax and the convergence of force is set to 0.001 eV/Å.
Results and discussion
Based on firstprinciples calculation, the lattice structure of αgraphdiyne is predicted for the first time, as shown in Figure 1. It clearly shows that αgraphdiyne has a hexagonal lattice the same as graphene. The optimized lattice constant is 11.42 Å. This is very insightful. On one hand, it has the largest lattice constant compared with currently known carbon allotropes [16] and thus has a much smaller density than graphene and other related carbon allotropes. This makes αgraphdiyne a potential candidate for hydrogen storage [17]. At the same time, the absorbed hydrogen may induce an intrinsic magnetism in the defected system [18,19]. On the other hand, this lattice constant has a very little mismatch with Si(111) surface, that is, one unit cell of αgraphdiyne matches the Si(111)3 ×3 unit cell well. This suggests that the high possibility is to grow αgraphdiyne epitaxially on Si(111) substrate. After the epitaxial structure is cooled down, one can remove the substrate by chemical etching. In this way, the isolation of monolayer αgraphdiyne might be obtained in experiments.
Figure 1. Crystal structure of αgraphdiyne.(a) A unit cell and (b) a 4×4 supercell. (c) A simplified model to mimic the hopping matrix elements along two carbon triple bonds in αgraphdiyne. Carbon atoms 1 and 6 are at vertices of a hexagon in αgraphdiyne. The black balls and blue line represent carbon atoms and the crystalline cell, respectively.
The band structure and density of states (DOS) of αgraphdiyne are shown in Figure 2a,b, respectively. The most important observations from Figure 2a are the linear dispersion near the K point and the zero DOS at the Fermi energy level. However, the corresponding slope of the Dirac cone is obviously smaller than that of graphene and αgraphyne. This has a big effect on the Fermi velocity, as discussed below. The bonding and antibonding orbitals at the Fermi energy level touch each other and develop two slight flat bands as K approaches M, which correspond to the two peaks near the Fermi level in the DOS plot. Similar to the case of graphene and αgraphyne, the Dirac points are located at the K and K^{′}, which means that there are even (six) Dirac points in the Brillouin zone, which is in a striking difference from the odd Dirac points observed in topological insulator Bi_{2}Te_{3}[20].
Figure 2. Electronic properties of αgraphdiyne.(a) Band structure and (b) DOS. (c) First Brillouin zone with the letters designating highsymmetry points. (d) 2D Dirac cone representing the valence and conduction bands in the vicinity of the K and K^{′} points. E_{F} is the Fermi energy.
Due to the breaking symmetry associated with spinorbit interaction (SOI) in 2D layered materials, a small band gap will be induced at the Dirac points, which can in principle be used to study the quantum spin Hall effect. The energy bands with SOI (not shown for brevity) open a band gap of 22 ×10^{3} meV in αgraphdiyne, and the magnitude is close to the value of graphene [21].
To understand the nature of the Dirac cone in αgraphdiyne, we employ the tightbinding method proposed in [22], where an effective hopping parameter is introduced. It is notable that there are six carbon atoms along the effective hopping direction in αgraphdiyne, as shown in Figure 1, while only four in αgraphyne. This makes it more complex to exploit αgraphdiyne than αgraphyne. To simplify the model, two triple bonds with the hopping parameters t_{1} and t_{2} for the single and triple carbon bonds are taken. The simplified Hamiltonian equations at the carbon triple bond, i.e., sites 2, 3, 4, and 5, are
where E and V are the electron and onsite energies, respectively. Based on Equation 1, we can easily obtain
When we focus on the electrons near the Dirac cone where E ≈ V, the wave functions are approximately φ_{2} ≅ (t_{1}/t_{2})φ_{4}, φ_{3} ≅ (t_{1}/t_{2})φ_{1}, φ_{4} ≅ (t_{1}/t_{2})φ_{6}, and φ_{5} ≅ (t_{1}/t_{2})φ_{3}. Thus, the hopping term from site 2 to 1 is
which means that the effective direct hopping parameter between sites 1 and 6 is
The obtained effective hopping parameter
Once we obtain the effective hopping parameter
where a is the lattice constant. By fitting the occupied and unoccupied bands in the vicinity
of the K point from the firstprinciples calculations, as illustrated in Figure 2a, the renormalized hopping parameter
It is known that the Fermi velocity plays a vital role in the photoelectric field and crucially dominates the transport properties. Here, we will focus attention on the study of Fermi velocity of αgraphdiyne. The dispersion close to the K and K^{′} points can be expanded as
where q is the momentum measured relative to the Dirac points, ‘ ±’ the upper and lower Dirac
cones, and v_{F} the Fermi velocity, given by
More information including the helical texture of Dirac cone and Berry’s phase are indeed associated with the detailed wave functions. In this work, we instead calculate the two orbitals at the Dirac point as shown in Figure 3. The charge density explicitly exhibits a 180° rotational symmetry, which is consistent with the theoretical conclusion in the literature [2]. The two orbitals consist of two types of bonds in αgraphdiyne: One is the bonding bonds (Figure 3a) and the other the antibonding bonds (Figure 3b), which are located at the different carbons. As a recent study reported [23], the effective hopping term of the acetylenic linkages is much smaller than the direct hopping between the vertex atoms. This is because the covalent bonds are formed in these acetylenic linkages as illustrated in Figure 3, which subsequently weakens the hopping ability. Thus, the reduced hopping parameter is a natural consequence, which also agrees well with our above tightbinding theory. Future experiments can test this prediction directly.
Figure 3. Charge density distributions of two orbitals at the Dirac point. The (a) bonding and (b) antibonding bonds. The isovalues are set to 0.03 Å ^{3}; 3 ×3 supercells are given for the sake of clarity.
Conclusions
In conclusion, we have predicted a novel carbon allotrope called αgraphdiyne, which has a similar Dirac cone to that of graphene. The lower Fermi velocity
stems from its largest lattice constant compared with other current carbon allotropes.
The effective hopping parameter
Competing interests
The authors declare that they have no competing interests.
Authors’ contributions
MSS designed the work and revised the paper. XNN calculated the firstprinciples results. XZM wrote the manuscript. DZY, ZYZ, and DSX have devoted valuable discussion. All authors read and approved the final manuscript.
Acknowledgements
We would like to thank L. Huang (LZU, Lanzhou) for the valuable discussion. This work was supported by the National Basic Research Program of China under no. 2012CB933101, the Fundamental Research Funds for the Central Universities (no. 2022013zrct01), and the National Science Foundation (51202099 and 51372107).
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