Two-dimensional octagon-structure monolayer of nitrogen group elements and the related

nano-structures
Yu Zhanga, Jason Leea, Wei-Liang Wanga, Dao-Xin Yaoa,b*
a
State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University,
Guangzhou 510275, China
b
Beijing Computational Science Research Center, Beijing 100084, China
*
Corresponding author: yaodaox@mail.sysu.edu.cn

ABSTRACT
In the purpose of expanding the family of two-dimensional materials, we predict the existence of two-dimensional
octa-structure of nitrogen group elements that are composed of squares and octagons in first-principle method based on
density functional theory (DFT). From our calculations, electronic structures of all monolayers show that they are
semiconductors with indirect (N, P, Bi) and direct (As, Sb) band gaps (0.57-2.61eV). Nano-ribbons of three different
unpassivated edges and their band structures are also investigated. Because of the reconstruction on the edges and
dangling bonds, there exist ferromagnetic edge states in P, As, Sb nano-ribbons with different edges, and a Dirac point
near π is found in the band structure of one specific N nano-ribbon. These structures may be useful in future applications,
such as semiconductor devices, spintronics, hydrogen storage and quantum computation.
Key Words: First-principle, Nitrogen group elements, Nano-ribbons, Edge state

1. Introduction their structures, as shown in Fig.1. There are five valence

electrons in one atom of VA elements, and each atom is
Since graphene was successfully exfoliated from graphite bonded to three neighbors similar to the honeycomb
in 2004 1 , numerous theoretical and experimental structure, so we expect them to have similar structure
researches have been invested in studying its properties2-5. parameters and properties.
Graphene possesses exceptional properties in many
aspects, especially for its electrical property on account of First-principle method based on density functional theory
the existence of Dirac electrons. Triggered by these (DFT) is used to investigate both monolayers and three
studies, a great number of graphene derivatives were different nano-ribbons with unpassivated edges. We
proposed and investigated in the past years, such as perform structure optimization to obtain stable structures,
graphane 6,7 , graphyne 8,9 , graphdiyne 10 , octagraphene 11 , and calculate the electronic structures to explore their
graphenylene 12 , 13 , and biphenylene 14 . Besides carbon, electronic and magnetic properties. 2D monolayers turn
many other elements can exist in two-dimensional (2D) out to be semiconductors with large band gaps, and
monolayers and exploring more 2D materials has great various reconstructions happen at the edge of
importance for various applications. nano-ribbons, which finally result in distinctive properties.
These properties can be used in future applications.
Phosphorus has many allotropes with different structures.
It is worth mentioning that a layered allotrope of 2. Computation methods and models
phosphorus, black phosphorus 15 - 17 , which has been
studied decades ago, is a semiconductor with a nonzero 2.1. Computational methods
band gap and high mobility. These properties make black In this paper, new octagon phases of VA elements are
phosphorus a better choice for applications18 compared studied in first-principle methods. Our calculation is
to other 2D materials, and it can be fabricated into based on Plane Augmented Wave (PAW) 25 , 26 with
field-effect transistors with excellent performance in Perdew-Burke-Ernzerh (PBE) of exchange-correlation as
room temperature19,20. In 2014, a new layered structure of implemented in the Vienna Ab initio Simulation Package
phosphorus, which has buckled honeycomb structure (VASP) code27. We use default plane-wave cutoff energy
similar to silicene, is investigated theoretically and named during the calculation. The Monkhorst-Pack28 scheme for
blue phosphorus21-23. It exhibits a much larger band gap k-point samplings with 15×15×1 mesh for planar sheets
than black phosphorus. In addition, honeycomb and 5×1×1 mesh for nano-ribbons were used to sample
monolayers of other nitrogen group (VA) elements (N, P, the Brillouin zone. A vacuum of about 15 Å thick is
As, Sb, Bi) are also predicted to exist24. inserted between two layers and two nanoribbons to avoid
Octagon and square structures can exist in carbon interactions. The structures are optimized until the
monolayers11-14 .In this work, we try to explore a new 2D remnant Hellmann-Feynman forces on the ions are less
allotrope of VA elements with octagons and squares in than 0.01 eV/Å. Spin-orbit Coupling (SOC) is included
only in the calculations of band structures of monolayers.

Fig. 1 (a) Top view and (b) side view of the investigated monolayer structure. The green square presents the unit cell, and the red arrows a1, a2 show
two basis vectors of the unit cell. There are 8 atoms in each unit cell. la and lb are two type bonds, and Δz is the buckled constant. (c) The first Brillouin
zone.
2.2. Computational models Fig. 1 (b)), we can see squares composed of interlace
buckled zigzags. There are 8 atoms per unit cell rather
We perform structure optimizations to obtain the stable than 4, that is because corresponding atoms in the
lattice structures shown in Fig. 1 (a) and (b). From the top adjacent squares are not in the same plane. The buckled
view (as shown in Fig. 1 (a)), the structures consist of octa-structure presents 𝐷4 symmetry different from the
squares and octagons instead of hexagons in their honeycomb structure. We calculate the bands of
honeycomb structures. The unit cell is a square, and the monolayers along Γ(0,0)-M(0,π)-X(π,π)-Γ(0,0) in the first
two basis vectors are given by a1=ai, a2=aj, where a is the Brillouin zone shown in Fig. 1 (c).
lattice constant. While from the side view (as shown in

Table 1 Structural parameters (unit in Å) of monolayers

Element a Δz 𝑙𝑎 𝑙𝑏

N 4.4187 0.6972 1.5173 1.4031

P 6.4564 1.2481 2.2723 2.2567

As 7.1020 1.4196 2.5267 2.5070

Sb 8.1326 1.6573 2.9088 2.8917

Bi 8.5972 1.7358 3.0606 3.0552

Optimized structural parameters of N, P, As, Sb, Bi are Comparing with parameters of the hexagonal structures,
listed in Table.1. a is the lattice constant, Δz is the bond length 𝑙𝑎 is a bit longer and 𝑙𝑏 is slightly shorter.
buckled constant as shown in Fig. 1 (b), la is the length of
bond in the square, and lb is the length of bond connecting As for the stability of monolayers, geometry
two squares, as shown in Fig. 1 (a). We can tell that optimizations present an energetically stable
lattice constant a, buckled constant Δz and bond length 𝑙𝑎 configuration for all the materials. For purpose of proving
and 𝑙𝑏 are all monotonously increasing with respect to the stability further, vibration frequencies at Г are
increasing atomic number from N to Bi, and are close to calculated to ascertain whether they are dynamically
the results of the honeycomb structures24. In addition, for stable, and there is no imaginary vibration mode. In order
all elements, bond length 𝑙𝑎 is larger than 𝑙𝑏 . to compare the stability of octagon monolayers and
hexagon ones, we calculate their cohesive energies band gaps from the calculations are listed in table.2. By
defined as 𝐸𝑐𝑜ℎ = 𝐸𝑚𝑜𝑛𝑜𝑙𝑎𝑦𝑒𝑟 − 𝐸𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 , which means comparing band structures with ((f)-(j)) and without
the energy difference between the energy of one isolated ((a)-(d)) SOC, we can see that SOC has no effect on band
atom and the energy of one atom in the monolayers. 𝐸𝑐𝑜ℎ structures of N and P. For As, Sb and Bi, SOC breaks
for octagon monolayers are -6.45eV (N), -5.20eV (P), energy degeneracy of bands from X to K. In addition, the
-4.50 (As), -3.91eV (As), -3.64eV (Bi). The cohesive effect of SOC increases as the atomic number of elements
energies per atom for octagon monolayers are slightly increases.
higher than that of the honeycomb counterparts, and the
As shown in Fig. 2, band gap decreases monotonously
energy differences are 0.36eV (N), 0.16eV (P), 0.14eV
from 2.61 to 0.57eV (0.26eV) without (with) SOC.
(As), 0.13eV (Sb), 0.12eV (Bi).
Without SOC, monolayers of N and P have indirect gaps
3. Results and discussion and monolayers of As, Sb and have direct gaps.The effect
of SOC of N and P monolayers is so small that we find no
3.1 Electronic Structure of Monolayers changes in our calculation. But for As, Sb, Bi, the band
gaps decrease obviously by including SOC. Furthermore,
Using DFT method, we calculate the electronic structures
SOC changes the gap of Bi monolayer from direct gap to
of the five VA elements with this special structure, as
an indirect one.
shown in Fig.2. They are all semiconductors, and the

Fig. 2 Band structures of (a)N, (b)P, (c)As, (d)Sb and (e)Bi without SOC and (f)N, (g)P, (h)As, (i)Sb, (j)Bi with SOC.

Table 2 Table 2 Band gaps (unit in eV) of monolayer of VA elements

Element Without SOC Gap type With SOC Gap type Change of band gap

N 2.61 Indirect 2.61 Indirect 0

P 1.95 Indirect 1.95 Indirect 0

As 1.70 Direct 1.59 Direct 0.11

Sb 1.33 Direct 1.05 Direct 0.28

Bi 0.57 Direct 0.26 Indirect 0.31

Fig. 3 1D Structure of each element with (a)type-1, (g)type-2 and (m)type-3 edge before optimization; optimized structure of (b)N, (c)P, (d)As, (e)Sb
and (f)Bi with type-1 edge; optimized structure of (h)N, (i)P, (j)As, (k)Sb and (l)Bi with type-2 edge; optimized structure of (n)N, (o)P, (p)As, (q)Sb and
(r)Bi with type-1 edge.

2.2 Three Different Nano-ribbons atoms at the edges, the band structures turn out to be
Intriguing.
We cut the monolayer to nano-ribbons with three different
edges from different directions and locations, as shown in Fig.4 shows the band structures of nano-ribbons with
Fig.3 (a), (g) and (m), and they are defined as type-1, three different edges. Spin-up bands and spin-down bands
type-2, and type-3. It needs to be stressed that the edges are degenerate, except for As, Sb with type-2 edge and P
are not passivated in our calculations. with type-3 edge. We notice that there are eight bands
near the Fermi level, the four bands above Fermi level
In this paper, we consider the three different nano-ribbons and the four bands below the Fermi level belong to
with 22, 24, and 24 atoms wide, respectively. Before the different spin components. From our calculations,
calculation of electronic structures, no less than four magnetic moments are about 4μB in the cases of
outermost atoms of each side were relaxed during the As(3.98μB), Sb(4.16μB) with type-2 edge and P(4.03μB)
structure optimizations. Reconstruction happens in many with type-3 edge. We analyze the charge density
cases, as shown in Fig.3 (b)-(f), (h)-(l), (n)-(r), and Bi (i), distributions of these eight bands, and find that the charge
P (l) with type-2 edge may not stable since bonds are of these bands is mainly distributed on the edges of the
broken after structure optimizations. It is interesting to nano-ribbon, as shown in Fig.5. We can conclude that
notice that the edge of N type-2 nano-ribbon (Fig. 3 (h)) these eight bands are corresponding to eight edge states
reconstructs to the structure with two adjacent squares which may be cause by dangling bonds.
stretch up and down. Because of the reconstruction of
Fig. 4 Band structures of nano-ribbons of (a)N, (b)P, (c)As, (d)Sb and (e)Bi with type-1 edge, (f)N, (g)As and (h)Sb with type-2 edge, and (i)N, (j)P,
(k)As, (l)Sb and (m)Bi with type-3 edge. Bands without spin polarization are plot in black lines. For (g), (h) and (j), black and red lines represent
spin-up and spin-down bands, respectively.
Fig. 5 Charge density distributions of the four bands under Fermi level of (a)P nano-ribbon with type-3 edge,(b) As nano-ribbon with type-2 and (c) Sb
nano-ribbon with type-2 edge edge. (d) Charge density distributions of the band above Fermi level of N nano-ribbon with type-2 edge, at 0, 0.2π, 0.4π,
0.6π, 0.8π and π, respectively.

It is interesting to notice that two linear bands seem the extraordinary rearrangement at the edge of the ribbon.
crossing at π in the first Brillouin Zone for N with type-2 We analyze the charge density of the band below Fermi
edge, which might indicate a Dirac point existing. To level at 0, 0.2π, 0.4π, 0.6π, 0.8π and π of the reciprocal
make further efforts, we calculate the band structure near vector to find that edge effect subducts from the edge to
π(0.98π~π), which reveals more exquisite image, as inside to a extent of about 0.7nm, as shown in Fig.5 (d).
shown in Fig. 6 (a). When SOC is not included, Fermi When SOC is included the Dirac point move to 0.9996π,
level exactly crosses the Dirac point at 0.9976π rather as shown in Fig.6 (b).
than π with zero gap. This special character is caused by

Fig. 6 Band structures of N type-2 nano-ribbon (a) without SOC, (b) with SOC
 Acknowledgements
4. Conclusions
The authors thank Wei-Feng Tsai, Fan Yang, and
We obtain the stable structures of the octagon phases of Feng-Chuan Chuang and for helpful discussions. This
VA elements based on first-principle calculation. 2D project is supported by National Basic Research Program
electronic structures show that they are semiconductors of China (2012CB821400), NSFC-11275279,
with band gaps that decrease monotonously from N to Bi. NSFC-11074310, Fundamental Research Funds for the
SOC, which is more important for heavier element, Central Universities of China, National Supercomputer
breaks energy degeneracy of bands. Center in Guangzhou, RFDPHE-20110171110026, and
By studying the nano-ribbons, we get various optimized NCET-11-0547.
edge reconstruction, and ferromagnetic edge states exist
in some cases with four spin-polarized bands lying both
below and above Fermi level. The rearrangement of
nano-ribbon of N with type-2 edge results in edge states
with a Dirac point near point π in Brillouin zone. These Appendix
distinct electronic properties may be cause by the In order to explore the orbital feature of bands, we
dangling bonds at the edges. calculate the projections of each band to s, p x, py and pz
Due to their intrinsic band gaps, 2D layers with orbitals, as shown in Fig. 7. Electrons in s orbital occupy
octagon-structure can be potential candidates in the the lowest eight bands without hybridizations to other
semiconductor devices, spintronics and quantum orbitals except for N, and we plot the lowest eight bands
computation. Besides, many 2D materials are studied in in red lines to represent s orbital. Above those s orbital
the aspect of hydrogen storage. Hydrogen is adsorbed by bands, px, py, and pz orbitals are dominant, which are
metal atoms attached to the surface of the materials. represented by three different colors. For P, As, Sb and Bi,
According to the previous calculations11, the hydrogen there is an energy gap between the top s band and the
storage capacity of octagraphene absorbed with Ti is 7.76 bottom p band, and the gap decreases from Bi to P,
wt%, which is close to that of graphene. Another 2D monotonously. In the case of N, two lowest band
carbon allotrope, biphenylene, can have a stronger branches overlap with each other, which lead to the
hydrogen storage capacity (11.6 wt.%) than graphene hybridization of s orbitals and p orbitals. We plot the
when Li is doped on its octagonal rings29. We expect that lowest eight bands in red for N (Fig. 7 (a)). It is worth
the monolayers of VA elements with octagon-structure mentioning that py orbital has the main contribution to the
can be a good candidate for hydrogen storage. bands near the Fermi energy, and the energies of px and pz
bands are lower than py band.
 Fig. 7 Band projections of (a)N, (b)P, (c)As, (d)Sb and (e)Bi monolayer to s, px, py and pz orbitals. Red lines correspond to s orbitals, three p orbitals
are presented in three symbols.
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