2 2D Monoelemental Materials

2D Xenes mainly refer to 2D monolayers of elemental materials composed

of group ⅢA, group ⅣA, group ⅤA, and group Ⅵ A.1 Up to now, 15 kinds of
monoelemental 2D layered materials have been experimentally and theoretically
con rmed. The general classi cation of emerging 2D Xenes and their corre-
sponding synthesis methods are presented in Figure 1.18, 9. Except for alumi-
nene and indiene which only exist as a theoretical prediction, all the other 13
elemental 2D forms have been successfully synthetized or fabricated.10 They
include borophene,11 aluminene,12 gallenene, and indiene in group IIIA,13, 14
silicene,15 germanene,16 stanene and plumbene in group IVA,17, 18 phosphorene,19
arsenene,20 antimonene and bismuthene in group VA,21, 22 and selenene and tel-
lurene in group VIA.1 And they have many excellent properties and applications,
including electronics, spintronics, optoelectronics, energy, and so on, as shown
in Figure 1.1.
The structure of a substance determines its properties. Symmetry, allotropes,
and orbital hybridization has vital effects on the structure. Here, we illustrate the
importance of symmetry, phase, and orbital hybridization of the structure by tak-
ing some 2D Xenes as an example.23 At the same time, the structure of 2D Xenes
are systematically classi ed and described.1 This paper is helpful for readers to
better understand the structure of monoelemental 2D materials and the effect of
structure on the application of properties, and provides some theoretical guidance
for their further research and development.

FIGURE 1.1 2D Xenes materials with their known synthesis methods and applications.
Elements shown in nattier blue and light sea green denote that elements have been pre-
dicted and have not been predicted from Xenes, respectively.
Structure/Classification of 2D Xenes 3

1.2 THE FACTORS OF 2D XENES’ STRUCTURES

1.2.1 SYMMETRY
Symmetry is the property of a crystal that has the same atomic structure in
corresponding directions, and in symmetric mirror relations along these direc-
tions, and that is similar in physical and crystallographic terms in two or more
directions. Symmetries in most crystals mainly include spatial translation, axis
rotation, center inversion, mirror inversion, and so on. Among them, spatial trans-
lation is the simplest symmetry of crystal materials. This symmetry is referred to
as long-range ordering, which is mainly described by hexahedral cell units sur-
rounded by three vectors on the atomic and molecular levels. Symmetry break-
ing refers to the phenomenon where asymmetry factors occur and the degree of
symmetry spontaneously decreases. Symmetry is ubiquitous in the system of all
scales. Symmetry breaking is the way of difference of things and any symmetry
must have symmetry breaking. Breaking symmetry and breaking defects are also
of great signi cance for structural exploration.
Among the physical properties of 2D Xenes, i.e., structural properties, are
some of the most unique properties compared to other non-2D materials. 2D
Xenes have ultrahigh surface area to volume. Different from three-dimen-
sional materials, two-dimensional materials are inherently constrained by the
degree of freedom in the direction perpendicular to the material. The buckled
structures of 2D Xenes make their atoms stronger in overlapping, leading to a
hybridized sp2-sp3 con guration with a lower symmetry and stability. Breaking
symmetry leads to novel physical properties. Xenes can be functionalized by
substrate, chemical adsorption, defects, charge doping, external electric eld,
periodic potential, in-plane uniaxial and biaxial stress, and out-of-plane long-
range structural deformation, to name a few.24 The electronic properties, includ-
ing the magnitude of the energy gap, can further be tuned and controlled by
external means.

1.2.2 ALLOTROPES
An allotrope is a substance composed of the same single chemical element but
with different properties, because the same element atoms are arranged in differ-
ent ways resulting in different physical and chemical properties of the structure.
The properties of 2D materials are dictated by their allotropes, how atoms are
arranged in the lattice. There are many allotropes in nature, and they have com-
pletely different physical properties. For example, graphite and diamond are typi-
cal allotropes of carbon.
The 2D materials have three kinds of crystal bonding structures, which are
simpli ed into the lattice diagram shown in Figure 1.2 (a), which is mainly
divided into three modes: hexagonal lattice, square lattice, and honeycomb lat-
tice. The bonds are the longest in the hexagonal lattice, intermediate in the square
lattice, and shortest in the honeycomb lattice, and the bond angles are 60◦ (hex),
4 2D Monoelemental Materials

FIGURE 1.2 (a) Schematic representations of the 2D lattices. The solid line indicates
the computational unit cells and dashed lines the Wigner-Seitz cells. (b) Structures for
phosphorus (α and β phase).

90◦ (sq), and 120◦ (hc). In 2D, the number of nearest neighbors is six for hexago-
nal, four for square, and three for honeycomb 2D lattices. Most metals are stable
in the hexagonal and honeycomb geometries, but unstable in the square-lattice
geometry. Most allotropes occur on nonmetallic elements, so allotropes are easy
to appear in 2D Xenes’ materials. For example, black phosphorus presents differ-
ent phases at different temperatures during the preparation process. At high tem-
peratures, as shown in Figure 1.2 (b), in each single atom layer, the phosphorus
atom forms a unique puckered structure (α phase) because two covalent bonds lie
parallel with the atomic plane while the third one is nearly perpendicular to that,
which plays an important role in bridge connection of phosphorus from upper
and lower layers. At low temperatures, black phosphorus transforms into a semi-
metallic β phase as seen in Figure 1.2 (b). It has been theoretically con rmed
that two types of buckling, low-buckled and high-buckled, exist among many
hexagonal 2D Xenes.
The effect of phase on structure has attracted scientists to further investigate
the allotropes of monoelemental materials and their excellent properties have
also attracted many scientists to conduct structural prediction research on 2D
Xenes’ materials. For example, He et al. used the RG2 method to search and
predict the two-dimensional graphene allotropes, and obtained 1116 new allo-
tropes.25 Meanwhile, the electronic properties of these two-dimensional graphene
allotropes were calculated by using the tight-binding method, and it was found
that there were 685 metal structures, 241 semiconductor structures, and 190 semi-
metal structures.26 The greatly enriches the properties and applications of two-
dimensional graphene allotropes.
Structure/Classification of 2D Xenes 5

1.2.3 ORBITAL HYBRIDIZATION

Orbital hybridization has an important in uence on the properties and applications
of structures. The bonding of atoms is very important because crystals are formed
by interactions between atoms. In this process, like all spontaneous processes in
nature, they tend to have the lowest energy of the whole system. This is because
the lower the energy, the more stable the system. To achieve this minimum energy
state, the bonding atomic orbitals have overlap as much as possible and increase
the number of bonds, that is, when the atoms interact with each other; only through
these two aspects can the energy minimum be achieved. So orbital hybridization
is essential. At the same time, after hybridization of orbitals, electron clouds are
more concentrated in the direction of bonding and more effectively overlap bond-
ing. Compared with pure s, p, and d orbitals, the bonding energy can be exerted
more effectively and the crystal structure is more stable. There are currently eight
basic types of orbital hybridization as shown in Table 1.1.
Different structures have different orbital hybridization states. For example,
the outermost electron con guration of a carbon atom is [He]2s22p2, which can
form a linear sp bond (alkyne bond), planar sp2 bond (ene bond), and tetrahedral
sp3 bond (alkane bond). Therefore, 3D block and 2D layered materials have differ-
ent orbital hybridization states. Taking 2D layered graphene as an example, a two-
dimensional hexagonal crystal structure is formed mainly by sp2 hybridization
between C atoms to form covalent bonds (as shown in Figure 1.2 (a)). The three
sp2 hybridized orbitals have the same shape and different spatial orientations. The
three one-electron sp2 orbitals on each carbon atom form σ bonds with each of the
three adjacent carbon atoms. The formation of a hexagonal honeycomb-like pla-
nar layered structure takes place. Each carbon atom also has a single electric sp
orbital that is not involved in the hybridization. These p orbitals are perpendicular
to the plane of the carbon sp2 hybridization orbital and are parallel to each other
to form delocalized large π bonds, making graphene have very good electrical
properties.

TABLE 1.1
The Type of Orbital Hybridization
Central Atomic Hybrid Type Atomic Configuration Type
sp Straight line
pd Straight line
sp2 Plane triangle
sp3 Tetrahedron
sp3d Tripartite biconical
sp3dz2dx2-y2 (sp3d2) Octahedron
sp3dxzdxydyz (sp3d3) Pentagonal biconical
spxpydx2-y2 (sp2d) Flat square
6 2D Monoelemental Materials

The 2D Xenes’ materials are mainly distributed in three, four, ve, and six
main groups and the electron con guration in the outermost atom is mainly s and
p orbitals. In contrast to graphene, 2D Xenes are not completely planar and fea-
ture a low-buckled geometry with two sublattices displaced vertically as a result
of the interplay between sp2 and sp3 orbital hybridization. Therefore, this paper
mainly analyzes the hybridization state of orbitals between s and p.23

1.3 THE CLASSIFICATION OF 2D XENES

1.3.1 GROUP Ⅲ
Group ⅢA in the periodic table, in column 13, has the shell electron structure of
[He]2s22p1. Among group ⅢA 2D Xenes, borophene (B), aluminene (Al), gal-
lenen (Ga), and indiene (In) have been studied in the recent literature. There are
many allotropes of these group ⅢA elements that have been theoretically pre-
dicted. This complexity could possibly be related to the lower number of three
valence electrons in group IIIA elements, resulting in their unique electronic band
structures. These structures are shown in Figure 1.3.
Boron is the only nonmetallic element in group IIIA. 2D boron (borophene)
properties have been probed theoretically by rst principles, and 2D boron

FIGURE 1.3 The allotrope structure of various elements atoms. Image for “8-Pmnn”
(Group IIIA) is reproduced from Ref. 31 with permission. Copyright 2019, Elsevier B.V.
Structure/Classification of 2D Xenes 7

allotropes with a large number of possible low-energy structures have been pre-
dicted.27, 28 These allotropes differ from their parent structure, the buckled tri-
angular boron, via concentration of vacant B sites as shown in Figure 1.3. These
allotropes are not all in a low-energy stable state.29 For example, free-standing
triangular boron and χ3 have been predicted to be dynamically unstable, with a
stability order of χ3> β12> striped triangular boron.30 It has been shown that 2D
boron is a metal, in contrast to its 3D crystal being a semiconductor. These boro-
phene allotropes have been con rmed by experimental studies, and they could be
obtained by mechanical cleavage, liquid-phase exfoliation, and vapor deposition
ways as shown in Figure 1.1.1
Aluminum (aluminene), gallium (gallenene), and indium (indiene) also have
shown different structures, as can be seen in Figure 1.1.1 Aluminene has been
studied and found in three different allotropes (planar, buckled, and curved).31 We
would like to note that these allotropes are stable crystal structures, and exhibit
metallic and semiconductor characteristics, respectively. Gallenene has also been
reported and shows two stable 2D con gurations (planar and curved). Gallenene
could be used by a simple stripping technique to peel a thinner 2D gallium layer
from the molten phase of Ga.32 Indium monolayers also have three different
allotrope forms (planar, puckered, and buckled).33 And the study shows that the
planar and buckled allotropes are stable and show metallic and semiconducting
behavior, respectively. The aluminene and indiene are currently only theoretically
predicted and have not been experimentally realized.1

1.3.2 GROUP Ⅳ
The group ⅣA 2D Xenes includes silicene (Si), germanene (Ge), stanene (Sn), and
plumbene (Pb).33–35 These four 2D Xenes possess similar electronic properties as
graphene because the shell electron structure of these 2D Xenes is the same as
graphene. But in obtaining hybridization of silicene, gallenene, and stanine, they
do not tend to undergo sp2 hybridization. Silicene is the rst and most widely
investigated of group ⅣA 2D Xenes. Contrary to graphene with sp2 hybridization,
free-standing silicene adopts a buckled hexagonal honeycomb structure.36 The
buckled Si atoms make themselves closer to enable a stronger overlapping, result-
ing in a hybridized sp2-sp3 con guration with lower symmetry.23 Germanene with
mixed sp2-sp3 hybridization leads to the buckled honeycomb structure.37 This
leads to all the 2D Xenes except graphene being not exactly planar, which is
called buckled structure as shown in Figure 1.3, which has a mixed degree of
sp2-sp3 character. The silicene and germanene are energetically more stable in the
low-buckled phase, while stanene and plumbene prefer the high-buckled phase
to become more stable. In comparison to graphene, the larger distance of atomic
bonding of germanene results in stronger spin-orbit interaction. Stanene has been
predicted to have a buckled honeycomb lattice structure.38
In fact, the reason that 2D Xenes are buckled rather than planar is that the hon-
eycomb planar lattice is not stable. The π-π overlap of four Xenes is much weaker
than in the case of graphene due to the larger atomic radius of Si, Ge, Sn, and Pb