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A theoretical review on electronic, magnetic and optical properties of silicene

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2016 Rep. Prog. Phys. 79 126501

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 Reports on Progress in Physics

Rep. Prog. Phys. 79 (2016) 126501 (57pp) doi:10.1088/0034-4885/79/12/126501

Review

A theoretical review on electronic, magnetic

and optical properties of silicene
Suman Chowdhury and Debnarayan Jana
Department of Physics, University of Calcutta, 92, Acharya Prafulla Chandra Road, Kolkata 700009, India

E-mail: cujanad@yahoo.com

Received 11 May 2015, revised 4 April 2016

Accepted for publication 23 May 2016
Published 18 October 2016

Abstract
Inspired by the success of graphene, various two dimensional (2D) structures in free
standing (FS) (hypothetical) form and on different substrates have been proposed recently.
Silicene, a silicon counterpart of graphene, is predicted to possess massless Dirac fermions
and to exhibit an experimentally accessible quantum spin Hall effect. Since the effective
spin–orbit interaction is quite significant compared to graphene, buckling in silicene opens
a gap of 1.55 meV at the Dirac point. This band gap can be further tailored by applying in
plane stress, an external electric field, chemical functionalization and defects. In this topical
theoretical review, we would like to explore the electronic, magnetic and optical properties,
including Raman spectroscopy of various important derivatives of monolayer and bilayer
silicene (BLS) with different adatoms (doping). The magnetic properties can be tailored by
chemical functionalization, such as hydrogenation and introducing vacancy into the pristine
planar silicene. Apart from some universal features of optical absorption present in all these
2D materials, the study on reflectivity modulation with doping (Al and P) concentration in
silicene has indicated the emergence of some strong peaks having the robust characteristic of
a doped reflective surface for both polarizations of the electromagnetic (EM) field. Besides
this, attempts will be made to understand the electronic properties of silicene from some
simple tight-binding Hamiltonian. We also point out the importance of shape dependence
and optical anisotropy properties in silicene nanodisks and establish that a zigzag trigonal
possesses the maximum magnetic moment. We also suggest future directions to be explored to
make the synthesis of silicene and its various derivatives viable for verification of theoretical
predictions. Although this is a fairly new route, the results obtained so far from experimental
and theoretical studies in understanding silicene have shown enough significant promising
features to open a new direction in the silicon industry, silicon based nano-structures in
spintronics and in opto-electronic devices.

Keywords: silicene, electronic properties, optical properties

(Some figures may appear in colour only in the online journal)

Nomenclature Armchair silicene nanoribbons—ASiNR

Armchair trigonal/triangular—AT
Antiferromagnet—AFM Band insulator—BI
Armchair graphene nanoribbons—AGNR Bilayer silicene—BLS
Aluminium oxide—Al2O3 Bowtie shaped—BS
Angle resolved photoemmision spectroscopy—ARPES Brillouin zone—BZ

0034-4885/16/126501+57$33.00 1 © 2016 IOP Publishing Ltd  Printed in the UK

Rep. Prog. Phys. 79 (2016) 126501 Review

Conduction band—CB Transition metal—TM

Carbon nanotube—CNT Triple vacancy—3V
Conduction band minima—CBM Treesaw silicene nanoribbons—TSiNR
Christmas-tree silicene nanoribbons—CSiNR Two dimensional—2D
Dangling bonds—DB Ultra high vacuum—UHV
Density functional theory—DFT Valence band—VB
Density functional tight-binding—DFTB Valence band maxima—VBM
Double layer—DL Van-der-Waals—vdW
Density of states—DOS van Hove Singularity—vHS
Diamond shaped—DS X-ray photon spectroscopy—XPS
Double vacancy—2V Zirconium diboride—ZrB2
Electron energy loss spectroscopy—EELS Zigzag silicene nanoribbons—ZSiNR
Electromagnetic—EM Zigzag trigonal/triangular—ZT
Field effect transistor—FET
Ferromagnet—FM
Free standing—FS 1. Introduction
Full width half maxima—FWHM
Generalized gradient approximation—GGA Two dimensional (2D) materials are always interesting in their
Giant magnetoresistance—GMR own right from a basic physics point of view, as well as in
Graphene nanoribbons—GNRs technology. There exist many layered materials having strong
Green’s function  +  (Screened) Coulomb interaction—GW in-plane chemical bonds but relatively weak coupling between
Hydrogenated bilayer silicene—HBLS the layers. These layered structures can be cleaved into indi-
Hexagonal boron nitride—h-BN vidual free standing (FS) atomic layers. These layers with one
Hyed–Scuseria–Ernzerhof—HSE dimension strictly restricted to a single layer (SL) are known
Hydrogenated silicene—H-silicene as 2D materials. In most inorganic materials, however, it is the
Inversion symmetry—IS quant­um effect which plays a key role in controlling the elec-
Infra red—IR tronic and optical properties. In such materials, both heat and
Local density approximation—LDA charge transport are confined to a plane. However, in addition to
Low energy electron diffraction—LEED this, in nanoform, the high surface to volume ratio also signifi-
Longitudinal gauge—LG cantly affects the chemical and mechanical response. In fact, the
Transverse gauge—TG all-surface nature of these 2D materials offers the opportunity
Molecular dynamics—MD to tune its properties by surface treatments, so called chemical
Molybdenum disulfide—MoS2 functionalization. Besides, the multifunctionality characteris-
Non-equilibrium Green’s function—NEGF tics of these materials is also one of the reasons it has received
Nonmagnetic—NM attraction from researchers. It is interesting to note that being
Nearest neighbor—NN just one atom thick, 2D mat­erials immediately appear as the
Next nearest neighbor—NNN most suitable candidate to create, eventually, a new generation
Nitric oxide—NO of electronic devices. These materials retain their 2D nature,
Perdew–Burke–Ernzerhof—PBE thus enabling an easy and direct processing to the mobile charge
Partial density of states—PDOS carriers and a very high carrier mobility both at room as well as
Pseudo Jahn–Teller—PJT at low temper­ature. Moreover, 2D crystals have two well-estab-
Photovoltaic—PV lished allotropes, SL and few layers. Besides, in such a class of
Quantum anomalous Hall effect—QAHE materials, doping is not continually necessary to alter the charge
Quantum spin Hall effect—QSHE carrier; local electric fields can also significantly modify the
Rashba interaction—RI charge carrier sign. In addition, the extreme thickness (smaller
Single vacancy—1V than the typical electric screening length of 5 Å) of these 2D
Single layer—SL mat­erials gives one an access to observe the variation in the con-
Silicene nanoribbon—SiNR ductance of the samples with a field. This is highly desirable for
Silicene nano mesh—SNM the applications in electronics and sensing. Note that in a 3D
Spin–orbit—SO graphite structure, the effect of an electric field in a mono- or
Spin–orbit coupling—SOC bi-layer is hidden by the behavior of the presence of the rest of
Spin–orbit interaction—SOI the layers. 2D materials with only one or a few atomic layers in
Sawtooth silicene nanoribbon—SSiNR thickness are favorable over bulk materials in terms of device
Scanning tunneling microscopy—STM scalability and the extension of Moore’s law [1].
Scanning tunneling spectroscopy—STS In recent times, one of the most exotic 2D materials in the
Tight-binding—TB material world has been graphene. In graphene, the valence
Tera hertz—THz band (VB) and the conduction band (CB) touch at a single
→
Topological insulator—TI point known as the Dirac point (K ). At this point, because of

2
Rep. Prog. Phys. 79 (2016) 126501 Review

the availability of a few number of electronic states, graphene Table 1.  Some important parameters of graphene, silicene and
is known as a semi-metal or zero band gap semiconductor. germanene.
The presence of this zero band gap, however, enables the absorp- Parameters Graphene Silicene Germanene
tion of light in a wide range of spectrums ranging from infra
red (IR) to ultraviolet. This opens up the possibility of using Lattice constant a (Å) 2.468 3.858 4.06
Bond length d (Å) 1.424 2.232 2.341
graphene in electro-photonic devices. Recent developments of
Buckling 0 0.42–0.45 0.69
graphene and other 2D material-based devices for flexible as
parameter ∆0 (Å)
well as stretchable applications have been reviewed by Kim et al Hopping 2.8 1.6 1.3
[2]. The diversity in electronic properties of the various 2D mat­ integral t (eV)
erials from the modern computational approach has been nicely Energy 0.02 1.9 33
reviewed by Miro et  al [3]. In particular, the role of various gap Eg (meV)
approximations in density functional theory (DFT) for comput- Fermi velocity 1.01 0.65 0.62
ing the band gap in these emerging 2D materials have been indi- v F(106 ms−1)
cated. The state of the art 2D materials beyond graphene, along Effective electron 0 0.001 0.007
with various states to prepare multilayer systems and characteri- mass m∗(m 0)
zation techniques, have been reviewed by Butler et al [4]. The λ SO (meV) 0.001 3.9 43
discovery of graphene [5–8] has fostered intensive research inter- Rashba 0.00 0.7 10.7
est in the field of graphene-like 2D materials, such as hexagonal interaction (meV)
∆E (eV) 8.7 7.2 8.1
boron-nitride (h-BN), silicene, germanene (hexagonal network
of silicon and germanium respectively), trans­ition metal dichal- Note: Reproduced with permission from [51]. Copyright (2013) by the
cogenides having a general structure of MX2 where M and X American Physical Society.
denote transition metal (TM) atom and oxygen family elements
respectively [9–11]. Until today, most of these mat­erials exist in Note that in graphene, there is no buckling at all. In terms
the hypothetical world, although several interesting theor­etical of ab initio calculations, this indicates that the structures of
works reveal various physical (electronic, magnetic, optical and Si with minimum energies could be obtained only when the
transport) properties of these materials [12–16]. These theoretical two atoms in a unit cell are not in the same plane, leading to
works naturally facilitate further insights in experimental synthe- a sheet that has ‘dimples or buckling’ rather than both atoms
sis and investigations of these materials. being in the same plane, as found for graphene. This buck-
It is natural to think of the existence of graphene as like the ling parameter ∆0 is defined as the vertical distance between
hexagonal network of group IV elements due to the similar the two planes of Si atoms. The original paper reporting this
electronic configuration of ns 2np 2. Si [[Ne] 3s 23p 2] lies below buckling of Si was published in 1994 by Takeda and Shirashi
C [[He] 2s 22p 2] in the same group in the periodic table, and [18]. The structural stability, along with the electronic struc-
therefore it has the same number of valence electrons. The ture, were explored in group IV elements C, Si and Ge by first
energy difference for carbon between 2s and 2p (10.66 eV) principles total energy calculations. The computations have
is almost twice [17] that of silicon (5.66 eV). Because of this yielded that C atoms preferred to form a D6h flat aromatic cage
difference in energies, there arises the difference in π bonding while Si and Ge formed a D3D corrugated aromatic stage. The
capabilities. As a consequence, Si tends to utilize all three of presence of imaginary frequency in the phonon dispersion of
its p orbitals resulting in sp3 hybridization. In other words, 3s planar silicene confirms its instability [19, 20]. In figure 2(a),
in Si can easily mix with all the subshells of 3p (3px, 3py, 3pz). we schematically depict the ball and stick models of graphene,
In fact, C activates one valence p orbital at a time as required silicene and germanene along with ∆0. A comparison of ∆0
by the bonding situation, giving rise to three possibilities of in these three 2D nanosheets (NSs) is summarized in table 1.
hybridization sp,sp2 and sp3. Because of this sp3 hybridization, Recent DFT calculations [19] predict two different bucklings
silicene is chemically more reactive compared to graphene. As of silicene— one is the low buckling (buckling height  ∼0.44 Å)
a result, electronic states can be easily tailored via chemical and another one is high buckling (buckling height  ∼2.15 Å);
functionalization. In fact, the reactivity is effective because however, the low buckled structure is observed to be more sta-
of the weak overlap between the 3pz of the neighboring Si ble than the high buckled structure. In contrast to graphene,
atoms. These weak bonds are easily broken when silicene, the band gap can be tuned in silicene by applying a transverse
a 2D elemental analogue of graphene, is exposed to foreign external electric field [21–23] without the need for any chemi-
atoms, such as oxygen and hydrogen. The difference of ener- cal functionalization. Besides, recently the tunable band gaps
gies (∆E) between the last shell s orbitals and p orbitals is have been observed in silicene-MoS2 heterobilayers [24] and
listed in table 1 for comparison. In figure 1, we schematically various substrates [25]. This phenomenon is advantageous in
depict the structures of silicene and the sp2 hybridization in device applications compared to graphene.
silicon. The major difference between graphene and silicene Chemical functionalization to silicene enhances the possibil-
lies in the fact that the planar silicene is unstable in contrast ity of its application in different branches. Hydrogenation as
to planar graphene. In contrast to graphene, it is to be noted well as fluorination of silicene can also open up a band gap,
that Si favors sp3 hybridization, whereas sp2 hybridization is although fluorinated silicene is observed to be more stable than
dominated in silicene. Therefore, the mixing of sp2 and sp3 the hydrogenated one [26]. A recent theoretical calcul­ation pre-
hybridization in Si results in a non-zero finite buckling (∆0). dicts that fully lithiated silicene exhibits a band gap opening

3
Rep. Prog. Phys. 79 (2016) 126501
Figure 1.  (a) 2D silicene (1 1 1) sheet. (b) Positions of the nearest neighbor (NN) atoms (c) sp2 hybridization in silicon.
of 0.368 eV [27]. It has also been demonstrated through DFT
calculation [28] that metal atoms bind to silicene with larger
binding energies than that of the graphene system. In the case
of graphene, B and N are two natural choices as a dopant as
these two elements are the nearest neighbors to C in the peri-
odic table, and moreover such doping strongly alters the elec-
tronic and optical properties of graphene [29, 30]. With this
motiv­ation, recently electronic properties [31] as well as opti-
cal properties [32] of aluminium (Al) / phosphorus (P) doped
silicene have been investigated in the framework of DFT. The
study of optical properties by varying the concentration of sub-
stituted Al, P and Al–P atoms in silicene NSs have indicated
[32] that, unlike graphene, no new electron energy loss spectra
(EELS) peak occurs irrespective of the doping type for parallel
polarization. Moreover, a vacancy in the silicene network can
also induce magnetism [31]. Edge geometry of silicene nano
disks substantially controls its optical properties [33]. Ciraci
et al [34] have extensively studied many aspects of silicene and
stabilization properties with respect to defects. These theor­
etical results valid­ate the promising usefulness of silicene in
future device applications, and it is also interesting to note that
silicene is indeed one step ahead compared to graphene due
to its compatibility with present matured silicon based semi-
conductor technology. However, in contrast to graphene (that
can exist in FS form), silicene has been grown only on metal
substrates (in general). Additionally, silicene always needs a
substrate for epitaxial growth due to its tendency towards sp3
hybridization. Silicene has been synthesized successfully on a
Ag(1 1 1) substrate [35–38], an iridium (Ir) (1 1 1) substrate [39]
and also on conductive ceramic ZrB2(0 0 0 1) [40]. First princi-
ples DFT calcul­ations have been employed [41] on electronic
properties of a silicene monolayer on various (1 1 1) semi-
conducting substrates, such as AlAs, AlP, GaAs, GaP, ZnS and
ZnSe to check the stability and bonding of the monolayer. The
electronic properties critically depend on whether the top layer
surface is metallic or non-metallic. For a non-metallic substrate,
the top layer undergoes p type doping while the metal substrate
undergoes n type doping, with the exception of GaP (1 1 1).
Recent progress in the growth of silicene and germanene has
been summarized by Kaloni et al [42]. The substrate interaction
of the grown silicon atoms on appropriate metal surfaces also
plays a key role in tailoring the band structure and their optical
4
Review
properties related to band structure and density of states (DOS).
This will help one to engineer the epitaxial silicene in the light
of future silicon based nanoelectronics.
1.1.  Importance of silicene over graphene
For several decades, it has been noticed that the bulk crystals
of group-IV elements, binary compounds of these elements
and group III–V compound materials have dominated the
microelectronic and optoelectronic industry. It is interesting
to know whether they may form a 2D honeycomb structure or
not. Based on structure optimization and phonon-mode calcul­
ations, Sahin et al [34] have pointed out that 22 different hon-
eycomb materials are indeed stable and correspond to local
minima on the Born–Oppenheimer surface. The calculations
have also revealed that all the binary compounds containing
one of the first row elements, B, C, or N, have planar stable
structures, while in the honeycomb structures of Si, Ge, and
other binary compounds, the alternating atoms of hexagons
are buckled since the stability is maintained by puckering.
Silicene is an emerging 2D material with the promise of
exhibiting Dirac physics like graphene, but of a larger spin–
orbit coupling (SOC). Along the column of the periodic
table (C → Si → Ge → Sn), the atomic weight increases from
12–119. This implies a strong relativistic effect as the veloc-
ity of electrons is proportional to the atomic number. This
has a two fold effect. Firstly, the low energy physics can be
described by a Dirac type energy-momentum relation simi-
lar to graphene. Besides, the presence of such Dirac fermions
also establishes a minimum (quantum) electrical conductivity,
even at a free carrier concentration of zero [6]. Thus, apart
from graphene, we have another prototype of a bench-top
relativistic quantum system in contrast to a conventional non-
relativistic system encountered often in a condensed mat-
ter system. The emergence of rich ‘Fermi-Dirac’ physics in
these 2D materials is associated with many unusual physical
→
properties. Due to its peculiar band structure near the K point
(Dirac point) in graphene, charge carriers behave like relativ-
istic particles with zero effective mass. The peculiarity (i.e.
a single point contact) makes the band structure of graphene
quite sensitive to any change, such as external electric fields,
mechanical deformations, doping and adsorbates, which is
Rep. Prog. Phys. 79 (2016) 126501
Figure 2.  (a) Comparison of ball and stick models of graphene, silicene and germanene adopted for numerical computations. (b) Band
structure of graphene (black), silicene (red) and germanene (blue).
desirable for any sensing applications. Angle resolved pho-
toemission spectroscopy (ARPES), often used to study the
distribution of electrons in reciprocal space, suggests that the
Fermi velocity of electrons in silicene (∼10 5 m/s) is almost
close or one order of magnitude smaller than that of graphene
(∼106 m s−1). Secondly, there is a significant increase in spin–
orbit splitting (λ SO) in comparison to graphene.
Compared to graphene, in silicene the spin–orbit interac-
tion is quite prominent and it eventually gives rise to a small
band gap (∼1.55 meV) opening at the Dirac point [43, 44]. In
other words, Dirac fermions are massless in graphene while
it is massive in silicene. Notably, this band gap value is far
from the present device application point of view, although
it helps for the emergence of a new field of research inter-
est regarding the phenomena of the quantum spin Hall effect
(QSHE) [44, 45]. Besides, in contrast to graphene, which does
not show QSHE, one can indeed observe QSHE in silicene
at relatively higher temperatures. Moreover, unlike graphene,
silicene is a topological insulator (TI) [46] characterized by
a full insulating gap in bulk with a helical gapless edge. The
coupled effect of a transverse tunable external field with the
spin–orbit interaction can transform silicene from a TI to a
band insulator (BI) [15]. In fact, the interplay of this SOC,
due to the buckled structure of these materials and a vertical
applied electric field, gives rise to a rich and complex variety
5
Review
of quantum phases, such as a topological or quantum spin Hall
insulator, a valley-spin-polarized metal, and a BI [47].
Besides, the overlap of π–π orbitals decreases by one order
of magnitude as one goes from C to Si due to the fact that the
atomic radius of Si is larger than that of C [17]. As a result,
Si–Si double bonds are comparatively weaker [48] than that of
C–C. Further, silicon’s covalent bonds do not have π stacking.
As a result, silicene does not cluster into a graphite-like form
[49]. Due to this structural modification, silicene has a lower
→
D3h symmetry (group of wave vector k at Γ point) instead of
the D6h symmetry of graphene.
→ →
For the Dirac or K point, the group of wave vectors k in
silicene and graphene is D3 and D3h respectively. Now one
may employ simple group theoretical arguments [50–53]
→
to explain the merging of the π and σ band at K (the Dirac
→
point) for graphene and silicene. The symmetry analysis at K
reveals [50] that rotation of the radius vector by
2π
anticlock-
3
→
wise is equivalent to the rotation of K in the opposite direction
(going to three equivalent corners of the Brillouin zone (BZ)).
Therefore, each basis vector is multiplied by the factor e23π i .
According to classical group theory [54], the two bands can
→
merge or cross at a point k 0 if there is a multi-dimensional
(higher than one) of the space group G0 realized at that point.
→
Within the framework of the degenerate k ⋅ p→ theory, we can
Rep. Prog. Phys. 79 (2016) 126501 Review

evaluate the energy eigenvalues ε (k ) from the wave functions

expanded in the basis as
2
Ψ(k ) = ∑ Ci(k )ψi(k 0 ).
(1)
i=1

The expansion coefficients satisfy the following relation given

by
→
k ⋅ p→ij 2
∑ m  Cj(k ) = ε (k ) Ci(k )
(2)
j=1

where p→ij =< ψi(k 0 )| p→ | ψj (k 0 ) > are the matrix elements cal-
culated in the basis wave functions. This is non-zero because
of the absence of the inversion symmetry (IS) at the k0 point
(the Dirac point in this case). The dispersion relation looks
like
ε (k ) = ∑ aαkα ± ∑ γαβkαkβ .
(3)
α αβ
The dispersion relation should contain those terms which
are invariant [53] with respect to all elements of G0, in this
case D3 for graphene as well as silicene. The group G0 or D3
does not contain any vector invariant; the only tensor invari-
ant turns out as k 2x + k 2y. Thus, the dispersion for silicene and
→
graphene at the K point reduces to a very simple linear form as
ε (k ) = ±vk.
(4)
For any tight-binding (TB) calculation related to band
structure, the first nearest neighbor (NN) hopping integral
(t) is necessary and the relevant values of t for graphene,
silicene, and germanene are listed in table 1. In figure 2(b), we
compare the band structure [55] of three important 2D NSs,
namely graphene, silicene and germanene. In the case of the
TB Hamiltonian [8, 9], velocity v can be related to t as v = 2
3ta
with a being the lattice constant. In the language of the Dirac
Hamiltonian, the equation  (4) is equivalent to the following
relations satisfied by px and py matrices
p2x = p2y ∝ I ; { px , py }+ = 0
(5)
where I is the unity matrix. These relations are necessary con-
ditions for the existence of Dirac points. When SOC is taken
into account (significant for silicene), although the lattice
→ →
symmetry and representation by the lattice functions (eik ⋅ Rj)
remain the same, one has to concentrate on the atomic term
rather than the atomic orbitals. Moreover, due to the semi-
→
integer value of the total angular momentum J , an additional
2
group element (Q, Q   =  E) is required for invariancy verifica-
tion. As a result, the four fold degeneracy (including spin) of
→
the bands merging/crossing at K is partially removed [50] due
to the SOC term. Hence, a non-zero gap-opening of silicene at
→
K is noticed. Importantly, the term arising in the Hamiltonian
due to the application of the vertical electric field in silicene
also removes the degeneracy, resulting in a non-zero finite
→
band gap at K . Thus, the linear band structure is the mani-
festation of long range hexagonal periodicity and sublattice
symmetry associated with the lattice.
Figure 3.  Buckling in silicene can give rise to possible structures
such as flat, chair, boat and washboard. (Reproduced with
permission from [12]. Copyright (2014) by John Wiley & Sons, Inc.)
In the wake of recent various 2D materials, it is legitimate
to make some brief comments regarding the scarcity of Dirac
cones in these systems. Dirac cones are indeed quite robust
against perturbation. In terms of these hopping integrals
(t1,t2,t3) a TB analysis on the honeycomb structure indicates
that the existence [56, 57] of Dirac cones is possible only
when the integrals form a triangle :
|t2 − t1| ⩽ | t3| ⩽ | t2 + t1| .
(6)
It is well known [58] that Dirac points are not only the
energy band crossing but are also related to singularities
in the concerned spectra of the Hamiltonian. The rarity
of Dirac cones can be explained from the von Neumann–
Wigner theorem [59, 60]. It turns out that in 2D materials,
the two real variables (kx, k y) are to be solved from three
equations. Since the number of variables is less than the
number of equations, the problem becomes overdetermined
resulting in no solution at all. This is the main reason that
the Dirac cones are not ubiquitous like defects in a system
but rare in 2D mat­erials. Thus, the existence of Dirac points
requires the reduction of the number of equations by sym-
metry, in particular, the space-time inversion symmetry [59,
60]. Again, the symmetry operation should be in such a way
→
that the K points remain invariant. Again, this fact does not
necessarily always guarantee the existence of Dirac cones.
Since kx and ky are real numbers they appear in the energy
eigen value E(k) in the form of sine or cosine. There may be
situations where, for a certain class of parameters, the solu-
tions may not exist. Finally, the Fermi level should lie at the
Dirac point and no other bands should go through this Fermi
level. If there is overlapping of other bands at the Fermi
level, then due to low energy excitations dominated by the
electron-hole carriers, it is difficult to detect the Dirac cones
experimentally. Except boron, most of the conditions are
satisfied in 2D bipartite systems with NN conditions. For
elusive discussions of Dirac cones in various 2D materials,
we refer the readers to a recent illuminating review article
by Wang et al [61].

6
Rep. Prog. Phys. 79 (2016) 126501
Moreover, it was also demonstrated clearly through an ana-
lytical calculation [62] that Dirac cones will appear whether
the 2D sheet is flat or dimpled. It is interesting to point out
that Dirac cones do not appear in hexagonal germanium in
contrast to silicene [63]. Besides, the calculation [307] of
the phonon modes clearly indicates the metastable nature of
the hypothetical flat surface of silicene. The buckled form
is indeed lower in energy by 30 meV/atom [34] and has a
binding energy of 4.9 eV/atom, which is about 0.6 eV/atom
lower than for bulk Si [307]. If we compare the band struc-
ture and total DOS for planar and buckled structures, we can
observe the presence of Dirac cones and the existence of a
→
zero band gap at the K point in the absence of SOC. This can
be explained via symmetry arguments [62]. In general, the
buckling occurs at various points in the unit cell, resulting in
different types of lattice arrangements, such as chair-, boat-,
and washboard-like structures (shown in figure 3). The DFT
calculations [64] have revealed that the boat- and washboard-
like structures are unstable, and they converge readily into the
flat structure. However, the chair-like structure remains more
stable than the flat one. Due to this peculiar distortion, some-
times it is stated that the hexagonal rings in silicene are in a
chair configuration.
In recent work carried out by Jose and Datta [49], the char-
acteristic chemical and structural properties of silicene have
been compared with graphene. In fact, the band gap opening
has been observed in silicene by applying an external trans-
verse static electric field. Buckling in silicene arises due to the
pseudo Jahn–Teller (PJT) effect in contrast to graphene. This
PJT arises by strong vibronic coupling of the lowest unoccu-
pied molecular orbital and highest occupied molecular orbital.
In fact, due to the closeness of the energy of these orbitals, they
are quite effective in causing the distortion to a high symmetry
configuration of silicene. However, this buckled structure can
be flattened by suppressing this PJT distortion. This can be
done by suitably doping atoms, such as lithium ions [49]. In
contrast to the pure graphene surface, the buckling nature of
the pristine silicene is also effective for catalytic active behav-
ior for nano Au20 clusters [65]. The band structure of silicene
is quite sensitive to the buckled atomistic structure and the
inclusion of many electron effects significantly modify the
band gap [66]. The finite bandgap of silicene sheets can also
be induced by the broken symmetry [67, 68].
With a tunable band gap, specific electronic components
could be made-to-order for applications that require specific
band gaps. Note that with graphene, being a semimetal, the
Eg
I heterostructures, electron transport from graphene to silicene
on–off ratio ( I On ∝ e k BT ) in typical field effect transistors
Off
(FET) is very small. It is worth noting that the bandgap of the
order of a few tens of meV is too weak for operation of FETs
at room temperature. In other words, graphene materials with
a large bandgap are necessary for room temperature (300 K)
operation of FETs. Again, because of the buckled structure
of silicene, few silicon atoms exist below and above the main
2D surface. Electrons in these regions possess distinct ener-
gies. As a consequence, by applying suitable electric volt­
ages, electrons can jump across this energy gap. This allows
silicene to move easily between the on and off state. In this
7
Review
respect, because of its tunable non-zero bandgap and buck-
ling, silicene is better than graphene.
Theoretically silicene FETs were first investigated by Ni
et al [308]. A dual-gated silicene FET has been constructed
with a SiO2 dielectric and a h-BN buffer layer. They have
allowed the control of both the doping level and the vertical
electric field applied to the monolayer. By applying a vertical
−1
electric field of amplitude 1 V Å at 300 K, the on/off ratio
has been found to be 4.2, which is rather low. The reason for
this low on/off ratio is because of larger leakage current in the
off-state due to tunneling . Adsorption of alkali metal atoms
is one of the feasible ways to open up a band gap which can
be utilized in making FETs. The physical reason behind using
alkali metal atoms is their ionic character. This ionic character
helps to prevent degradation of unique electronic properties
of silicene. Quhe et al [69] have used sodium atoms as alkali
atoms for FET modelling. By using sodium atoms they have
achieved the (essential) required on/off current ratio (4 × 108)
for high speed logic applications. Another candidate for mak-
ing silicene FETs is silicene nano mesh (SNM). This is built
by digging a simple triangular array of hexagonal holes in a
silicene sheet. Detailed first principles calculations [70] have
demonstrated clearly that a suitable mass band gap (<0.15 eV
for strain) can be opened in SNM by bond symmetry break-
ing and uniaxial strain. The gap increases up to a critical uni-
axial strain of 7% and then decreases. The maximum values of
mass band gap are, however, dependent on the defect density
in SNM. The maximum band gap of SNM has been found to
be 6.8 eV, perfectly suitable for FET applications. Utilizing
this SNM in a single gated FET by suitably adjusting the volt­
ages, Pan et al [71] have achieved the on/off ratio of 5.1 × 10 4.
This value is about three orders of magnitude larger than the
maximum on/off ratios obtained in dual-gated silicene FETs.
But the main drawback of using SNM as FETs is that at room
temperature, the on/off current ratio is decreased to 100 due
to phonon scattering. Wang et al [72] have indicated another
(alternative) way to use silicene as an FET. By stacking 2D
Dirac materials forming heterostructures vertically, one can
open up a transport gap in the transmission spectra. As an
example, Wang et al [72] have constructed a graphene/silicene
stacked heterostructure and have observed a large transport
gap of over 0.4 eV of a single-gated two-probe model. Here
the achieved on/off current ratio rises up to 106. Although
both of the materials involved here possess a zero band gap,
the stacked composite material shows a large on/off ratio.
The reason behind this lies in the fact that in Dirac material
and vice versa near EF is forbidden without the assistance
of a phonon, due to momentum mismatch. This momentum
mismatch is responsible for this composite material possess-
ing the transport gap in the transmission spectra. Li et al [73]
have investigated the applicability of a silicene nanoribbon
(SiNR) as an FET. From their study, it has been revealed that
the on/off ratio depends on the width of the nanoribbon. This
is expected as the band gap in SiNR also depends on the width
of the nanoribbon. It has also been indicated that in armchair
silicene nanoribbon (ASiNR), the on/off current ratio can be
tuned up to 106.
Rep. Prog. Phys. 79 (2016) 126501
Tao et al [74] have reported the first experimental evidence
of a silicene FET operating at room temperature. The experi-
ments were performed at high vacuum because it is known
that there are some issues regarding the stability of silicene
in air. The authors have devised a new technique called the
synthesis-transfer-fabrication process to overcome this seri-
ous stability issue. The epitaxial silicene has been synthesised
on Ag(1 1 1) thin film on a mica substrate [75]. The authors
have noticed a linear drain current (Id) versus drain voltage
(Vd) relation which indicates ohmic contact under ambi-
ent conditions. To estimate the on/off ratio, they have plot-
ted Id or R (= Vd /Id) versus back gate voltage (Vg). From the
experiment, their estimated on/off ratio is about one order of
magnitude. The overall electron mobilities of their devices
have turned out to be  ∼100 cm2 V−1 s−1. This value is lower
than that of graphene under the same device configuration. A
possible explanation for this low estimated mobility can be
provided in the light of acoustic phonon scattering present in
silicene [75]. This scattering mechanism is absent in planar
graphene. In graphene, due to its intrinsic reflection symme-
try, it can suppress the out-of-plane acoustic phonons. But
the buckling present in silicene breaks this intrinsic reflection
symmetry, resulting in strong out of plane phonon scatter-
ing. Although in FS silicene, theoretically predicted electron
mobility is  ∼1000  ∼  100 cm2 V−1 s−1 [76], here the substrate
affects the mobility because of acoustic phonon scattering and
electron–phonon coupling in all the devices. For more details
about silicene FETs, the readers are encouraged to consult the
review article by Ru-Ge et al [77].
Si atoms are very soft in nature. They can bond easily with
other foreign atoms and, in particular, they react strongly with
oxygen rendering oxidization easy. In addition to this poten-
tial compatibility with existing semiconductor technology,
silicene has the extra advantage that its edges do not exhibit
oxygen reactivity [78]. Alkali metal-doped silicene can only
produce n-type semiconductors while Ir doped silicene allows
a p-type semi-conductor. Again through platinum (Pt) dop-
ing, neutral (i-type) silicene is possible [308]. Further, with
the increase of the size of silicene, the reorganization energy
decreases due to structural relaxation in electrons or holes
[49]. Therefore, with the combination of n-type, p-type and
i-type doped structures, silicene has substantial opportunities
for use in electronics.
Another interesting derivative of silicene, formed from the
full hydrogenation of silicene, is known as silicane. The edge
Si atoms in silicene are all saturated with H or F atoms to
avoid the effects of dangling bonds (DBs). Since FS silicene
is a low buckled structure, it may be possible to favour sp3
hybridization through Si–H bonding with enhanced buck-
ling. With this motivation, the full hydrogenation of silicene
(2 3 × 2 3 )R 30 has been explored [79] by DFT calcul­
ation and scanning tunneling microscopy (STM) images. As
a result, synthesis of half silicane (one Si sublattice is fully
H-saturated and the other sublattice remains intact, forming a
perfect 1 × 1 structure) will trigger the investigation regarding
other unexplored electronic and optical properties. The scan-
ning tunneling spectroscopy (STS) measurements suggest that
the DOS of hydrogenated silicene (H-silicene) is substantially
8
Review
decreased from the EF to 0.6 eV compared to silicene, indicat-
ing an opening of the gap. This pioneering work will be useful
for controllable hydrogen storage. The hydrogen-terminated
germanium multilayered graphane analogue, germanane has
also been synthesized [80] from the topochemical deintercala-
tion of CaGe2. In fact, the incorporation of hydrogen atoms is
the standard method for saturating DB. Silicene’s hydrogena-
tion reaction is more exothermic than graphene. Since this
hydrogenation of silicene to silicane is exothermic, it is envis-
aged that most probably silicane can be used as hydrogen stor-
age. The band structure calculations by Guzman-Verri et  al
[81] have indicated that silicane is an indirect semiconductor
with a band gap of the order of 2.2 eV. Upon adsorption of
hydrogen, the structure undergoes a transition from sp2 to sp3.
That is why an energy gap appears in silicane. In par­ticular,
silicane is predicted to have an indirect gap (3.8–4.0 eV) for
chair-like structures but a direct gap (2.9–3.3 eV) for boat-like
structures. Similarly, hydrogenated germanene known as ger-
manane is expected to possess a direct gap for both chair-like
(3.5–3.6 eV) and boat-like (2.9 eV) structures [82, 83]. Note
that these structures are considered as wide bandgap structures
in comparison to their intrinsic bulk counterparts silicon and
germanium (where bandgap values are  <1.2 eV). In table  2,
we compare the various electronic and structural parameters
for these hydrogenated 2D structures. Note that germanane
is a direct band gap semiconductor, whereas, depending on
their atomic configurations, chair-like and boat-like silicanes
were determined to be indirect and direct semiconductors,
respectively. Recent calculations based on DFT and molecular
dynamics (MD) have indicated that the band gap in silicene
can be tailored by hydrogenation ratio [84, 85], halogena-
tion and lithiation [14]. The experimental bands of hydrogen-
ated (2 3 × 2 3 ) silicene phase on Ag(1 1 1) can be closely
reproduced via DFT calculations [86].
The thermoelectric effect is nothing but the conversion
of a temperature gradient across a material into an electrical
current, and is controlled by electron–phonon drag through
the material. The relevant parameter which measures the effi-
ciency of this process is known as the thermoelectric figure of
S2σT
merit, ZT th = κ , where S, σ and κ denote the Seebeck
coefficient, electrical conductivity and thermal conductivity
respectively. It is worth pointing out that for optimal ZT th in
conventional thermoelectric application, material should have
large σ and S with low κ. Values of ZT th greater than equal to
1 are desirable for energy generation. Although the electrical
conductivities (σ) of graphene and silicene are comparable,
however, S is smaller in graphene compared to silicene. Also,
κ has a large value in graphene as compared to silicene. As a
result, ZT th of silicene is substantially higher than graphene.
Theoretical computation yields a value of ZT th close to one
for pristine silicene while suitable n-doping or p-doping can
enhance this value up to 2.8 [87]. This eventually indicates the
promising thermoelectrical prospect of silicene in contrast to
graphene.
The mechanical strains can effectively tailor the band struc-
ture of graphene and other 2D hexagonal structures [88–91].
Mohan et al [92] have demonstrated that a direct band-gap of
Rep. Prog. Phys. 79 (2016) 126501
Table 2.  Important parameters of graphane, silicane and
germanane.
Parameters Graphane Silicane Germanane
Lattice constant a (Å) 2.514 3.820 4.091
Metal–metal distance d (Å) 1.520 2.319 2.338
Metal–hydrogen distance (Å) 1.084 1.502 1.530
Buckling parameter ∆0 (Å) 0.45 0.72 0.69
Energy gap Eg (eV) 4.9a, 5.4b 2.9a, 4b 2.9a, 3.6b
Fermi velocity v F(106 ms−1) 0.63 0.51 0.38
a
Boat-like structures, bchair-like structure.
Note: Reproduced with permission from [12]. Copyright (2014) by John
Wiley & Sons, Inc
389 meV is possible for 6% of uni-axial compression while an
indirect band-gap of 379 meV is possible for 6% of bi-axial
compression. Further increase of strain beyond 8% silicene
is, however, changed into metal. Choi et al [93] have demon-
strated that strained graphene (up to a large uniaxial strain of
30%) does not develop an energy gap and the group velocities
under uniaxial strain exhibit a strong anisotropy. Besides, it
has also been noticed that the work function of strained gra-
phene increases substantially as strain increases. Hu et al [94]
have observed a rapid increase of Poisson’s ratio with an axial
strain in comparison to a steady decrease in the case of gra-
phene. This mechanical flexibility in silicene can be argued in
terms of changing bond angle rather than bond length. In gra-
phene, however, the bond length is seen to increase with the
application of axial strain. This superior mechanical flexibility
of silicene in comparison to that of graphene may be useful for
flexible nanoelectronics.
But the main disadvantage is that sp2 bonded Si is much
less common than for C, and as a result, the synthesis of Si in
a graphene-like structure is far reaching. Again the study [95]
of the cohesive energy of Si nanotubes indicates that only 82%
of that of bulk silicon is in a diamond structure. This should
be compared to 99% of carbon nanotubes (CNT) versus crys-
talline graphite. This points out the essential difficulty in pro-
ducing Si NTs and especially silicene. Again, because of the
preference of sp3, physical exfoliation like graphene is impos-
sible, and in nature, layered silicene does not exist. Thus, for
the synthesis of silicene, a substrate plays a key role in con-
trolling the effective van der Waal (vdW) interactions [96].
1.2.  Some recent developments and scope of this review
The review article by Balendhran et al [12] critically discusses
the four major emerging classes of 2D elemental materials :
silicene, germanene, stanene, and phosphorene—with empha-
sis on the fundamental properties and synthesis techniques.
In the recent review articles [13, 16, 49] of silicene, the syn-
thesis and structural analysis along with some band structures
have been discussed. The electronic band structures of silicene
NSs having chemical functionalization with hydrogen have
been compared [8] in various DFT and TB models. However,
no review articles are available at present discussing the optical
and magnetic properties of doped and defected silicene (planar
or buckled). Nevertheless, the various optical properties can
9
Review
Table 3.  Rashba spin–orbit coupling λ R2 in meV unit.
Si Ge Sn Pb
8.66 2.81 18.75 0.06
Note: Reproduced with permission from [105]. Copyright (2013) by Nature
Publishing Group, courtesy of Thomson Reuters.
be understood from the band structures of relevant structures.
Apart from this, the magnetic properties of silicene nano-
disks can also be understood from some basic principles. We
strongly believe that being armed with these theoretical pre-
dictions from DFT will enable the experimentalist to synthe-
size the stable structures and look for appropriate silicon based
nano-structures in spintronics and opto-electronic devices.
Considerable modulation of the band gap by an external electric
field in silicene-based hetero-bilayers, such as graphene, BN
has been noticed [97]. A recent review article by Houssa et al
[98] regarding the experimental and theoretical investigation
of silicene has emphasised the structural, electronic and vibra-
tional properties of FS silicene. The stable phases of silicene
focussing on the electronic band responsible for the existence
of Dirac fermions have been reviewed [99]. This is important
for device processing using the growth of silicene monolayers
or multilayers in metal or non-metal substrates. First princi-
ples DFT [100] has been utilized to show the dynamical stable
structure for silicane and germanane, and the appropriate tight
binding model to describe the band structure. The TB results
of the band structure have been compared [101] with ab initio
calculations to construct the effective Hamiltonian of silicene
in the vicinity of the Dirac point.
2.  Tight binding model for the buckled system
To understand some important features associated with
band structure and to have an insight into the underlying
physics, we would like to introduce the minimal discrete
TB Hamiltonian relevant for the buckled system, such as
phosphorene, silicene and germanene. Moreover, this TB
model will help us to relate some of the experimental data.
Nevertheless, this model has also been used to discuss the
topological phase transition and zero modes [47, 102, 103].
We will closely follow the following works [43, 44, 53, 93,
104–106] most relevant for this section. The TB and first
principles calculations in silicane and germanane have been
nicely reviewed in recent literature [100].
The basic →physics of silicene around two inequivalent
→
points K and K ′ in the first BZ can be described by the four
band model as
iλ SO
H0 = −t ∑  C†iαCjα + 3
3
∑ vij  C†iασαβ z
Cjβ
〈ij〉α 〈〈ij〉〉α, β
(7)
2iλ R2
− ∑  µi  C†iα(σ→ × dˆij )αβ
3 〈〈ij〉〉α, β
z
Cjβ.
Here, C†iα(Ciα ) creates (annihilates) an electron at site i with
spin polarization α. The operators satisfy the following anti-
commutation algebra given by
Rep. Prog. Phys. 79 (2016) 126501
{C†iα, Cjβ} = δijδαβ , {Ciα, Cjβ} = 0 = {C†iα, C†jβ}.
(8)
Now, the symbol ⟨ij⟩(⟨⟨ij⟩⟩) denotes the NN (next nearest
neighbor (NNN)) interaction hopping sites. The first term in
the Hamiltonian (7) indicates the NN hopping on the respec-
tive honeycomb lattice. The second term (complex) represents
the effective SOC interaction with σ z being the z-component
of Pauli spin matrices. λ R2 denotes the coefficient of Rashba
spin-orbit interaction (SOI). The typical values of the hopping
integral t and λ SO for silicene are taken as 1.6 eV and 3.9 meV
respectively. This term respects the IS. The third term in the
Hamiltonian (7) represents the second Rashba SOC (please
see table  1 for comparison with silicene, graphene and ger-
manane) with λ R2 = 0.7 meV associated with the NNN hop-
ping term. Here, µi = ±1 for the A (B) site, and dˆij = dij / | dij|
→ →
→
with the vector dij connecting two sites i and j in the same
sublattice. Note that the Rashba interaction (RI) respects the
IS but breaks z → −z mirror symmetry. These second and
third terms are important for silicene because of the presence
of non-zero finite buckling. Note that the Rashba SOC term
→ →
makes no contribution at the Dirac points (K , K ′). The impli-
cations of Rashba SOC in condensed matter physics have fos-
tered the interest for both physicists and material scientists in
the development of inversion asymmetric structures required
for layered graphene-like structures to cold atoms [107, 108].
By performing Fourier transformation, we can obtain the
low energy effective Hamiltonian [43] around the Dirac point
→
K , and in particular, we can obtain an expression for the Fermi
3 at →
velocity v F = 2 at the Dirac K point where a is the lat-
tice constant. In 2D, Rashba SOC looks like α(σ xk y − σ ykx )
with α being a constant. For a typical Hamiltonian
2k 2
HR = 2m
+ α(kx + ik y ), it is simply,
⎛ 2k 2 ⎞
⎜ α (k x + i k y ) ⎟
HR = ⎜ 2m ⎟ spin-polarized quantum Hall effect and topological supercon-
⎜ ⎟
⎜ α (k x − i k y ) ⎟
2k 2
⎝ 2m ⎠ in the presence of an electric field Ez.
2k 2
with eigenvalues E± = 2m ± αk.
Due to the buckled structure in silicene, the two sublat-
tice planes are separated by a distance, which we denote by
2l = ∆0 with l = 0.23Å. It generates a staggered sublattice
potential (∆) of the form ∆ = 2lEz between silicon atoms at A
sites and B sites. The two additional terms in the Hamiltonian
for the electric field can be incorporated as
Helec = iλ R1(Ez ) ∑ C†iα(σ
→
× dˆij )αβ
z
Cjβ + l ∑  µiEzi  C†iαCiα.
⟨⟨ij⟩⟩α, β iα
(9)
The first term in the equation  (9) is the Rashba SOC NNN
hopping term induced by the electric field and λ R1(Ez ) ∝ Ez,
and becomes of the order of 10 µ  eV at Ez = λ SO /l = 17 meV
−1
Å . Thus we notice the existence of two Rashba type interac-
tions in the Hamiltonian. Owing to the low buckled structure
in silicene, the term in the equation  (9) is known as intrin-
sic SOC while that in equation (7) is due to an external elec-
tric field. The second term in (9) is known as the staggered
10
Review
sublattice potential term ∝2Ez between silicon atoms at A sites
and B sites and breaks the symmetry between the A and B
sublattices of the honeycomb structure. We will notice later
the consequence of the breaking of this symmetry. Moreover,
the external electric field breaks the real space IS which is
equivalent to sublattice breaking symmetry. Another way of
breaking this symmetry is by applying mechanical strain. The
mechanical strain can break the 6-fold rotational symmetry
into 3-fold rotational symmetry. These terms are responsible
for the microscopic responses to the external electric field.
This electric field can be interpreted as the net electrostatic
difference arising from both the external fields, the presence
of the substrate and localized impurities.
The Zeeman (exchange) term can also be included in the
Hamiltonian (preferably as perturbation) as
Hmag = M ∑ C†iασαβ
(10)
z
Cjβ.
i
Due to the application of a local exchange field M in the
z-direction (out of plane), this term eventually breaks the local
time-reversal symmetry on the upper edge of the sample. This
local exchange field M may originate due to close (proxim-
ity) coupling to a ferromagnet (FM), such as depositing Fe/
Co/Ni atoms to the surface of the upper edge of the silicene
nanoribbon or depositing SiNR partially to an FM insulating
substrate.
Another perturbing potential known as Haldane induced by
photo-irradiation in the sample can be inserted [103, 110] in
addition to the above terms as
iλ Q
Hph =
(11) ∑ vij  C†iασαβ
3 3 〈〈ij〉〉α, β
z
Cjβ ,  λQ = v2F A 2 Ω−1
where A is dimensionless intensity and Ω is the frequency. In
fact, this term is responsible for the emergence of new phases
(such as the photo-induced quantum anomalous Hall effect,
ductors) [109] by applying circular polarized light to silicene
A regular onsite term can also be added to the Hamiltonian
H0 to take into account the random disorder in the silicene net-
work [106]. This additional term can be of the following form
Hdis = ∑ εiC†iαCiα.
(12)
i
Here, εi = E0 + wi is the onsite energy. E0 in this case is the
energy of the Dirac point which is set to zero as the energy of
the zero-point and wi is the onsite disorder energy uniformly
distributed in the range [−w/2,w/2] with disorder strength w.
The full TB Hamiltonian is then given by
H = H0 + Helec + Hmag + Hph + Hdis.
(13)
The qualitative understanding of band structure from first prin-
ciples calculations can be understood from the interplay of
these terms in the above Hamiltonian. The interplay of vari-
ous terms gives rise to various quantum anomalous Hall insula-
tor, TI/semimetal/metal phases [110]. It is interesting to point
out that graphene is described by the above Hamiltonian with
λ SO  =  0  =  λ R2 along with the absence of Helec and Hph in the full
Rep. Prog. Phys. 79 (2016) 126501
TB Hamiltonian in equation (13). The above Hamiltonian with
suitable parameters can be applied to other generic 2D buckled
systems. Fitting results for Rashba SOC from first principles
calculations for various 2D structures are shown in table 3.
It is interesting to note that the TB Hamiltonian with the
NNN hopping and SOC term is invariant under particle-hole
transformation. However, with the addition of Rashba interac-
tion, the symmetry is broken. Besides, the staggered poten-
tial term (second term in Helec) also breaks this particle hole
symmetry. As a result, silicene undergoes a topological phase
trans­ition with the help of an electric field from QSH to a
trivial insulator [102]. In fact, a topological superconductor
can be realized in a honeycomb system (silicene, germanene,
stanene (2D elemental analogue of tin)) by incorporating
photo-irradiation and s-wave superconductivity proximity
coupling [111].
The low energy effective Hamiltonian of silicene around
the Dirac point (Kη) with η = ±1 can be derived [43, 102]
from the above TB Hamiltonian as
H Oη = v F(ηkx + k yτy ) + λ SOσzηkz + aητzλ R2(k yσx − kxσy )
= v F(ηkx + k yτy ) + ητzh11
(14)
h11 = λ SOσz + aλ R2(k yσx − kxσy ).
Here, τa is nothing but the components of Pauli matrices act-
ing on the pseudo spin space associated with A and B sublat-
tices. Similarly, the other terms in the Hamiltonian also can
be recast as
H ηelec = lEzτz + λ R1(ητxσy − τyσx )/2
H ηph = λQητz
(15)
H ηmag = Mσz = m stagσzτz + mavgσz
m −m m +m
where m stag = A 2 B and mavg = A 2 B with mA(mB) is the
corresponding sublattice A(B) magnetization. In the presence
of only an electric field (H ηph = 0 = H ηmag) and without the
presence of any onsite disorder, it is easy to be convinced that
the bandgap is located at the Dirac point. The gap at the Dirac
point is given by 2|∆s (Ez )| with
lEz 1 most importantly, the growth process, such as in the chemical
∆s (Ez ) = −sλ SO +
(16) + (lEz )2 + λ2R1 .
2 2
Moreover, since λ R1(Ez ) ∝ Ez, it has been noticed that with
the increase of Ez, the gap decreases linearly with Ez, and there
is a critical electric field Ec at which the band gap vanishes and
the magnitude of Ec in terms of the parameters turns out as
sλ ⎡ ⎛ λ R1 ⎞2⎤
Ec = SO ⎢1 − ⎜ ⎟ ⎥ = ±17  meV Å .
−1
l ⎢⎣ ⎝ 2λ SO ⎠ ⎥⎦
(17)
A careful look reveals that the possible terms in the Hamiltonian
can be written in a compact notation [110] Hpqr = λ pqr η p(σz )q (τz )r
with λ1 1 1 = λ SO, λ 0 0 1 = −lEz, λ1 0 1 = ΛQ and λ 0 0 1 = m stag.
In this notation, the Dirac mass can be read as
∆σηz = ησzλ SO − lEz + ηλQ + σzm stag. The system undergoes a
phase transition from TI to a non-TI depending on the mag-
nitude of λ SO and lEz in the limit λQ = 0 = m stag. In fact
11
Review
λ SO = l | Ez| demarks the critical point where the closing of the
energy gap occurs. Thus, the sign change of the mass term
indicates the inversion between CB and VB. As a result, the
directions of τ→ and σ→
of CB and VB change. Like graphene
[93], one can also study the effect of strain in silicene in this
TB Hamiltonian. In that situation, the hopping integrals from
the unstrained case will change accordingly depending on the
positions of the NN atoms. The influence of the exchange field
on the transport properties [106] of SiNR has been probed in
the presence of disorder potential. The Hamiltonian approach
has been adopted to show that a silicene pn junction is an
FET with quantized conductance [112]. In contrast to the
graphene pn junction, the silicene junction can emerge as a
new device controlled by two types of electric field V and Ez.
When 3D TMs are deposited on the stable adsorption site,
in that situation the induced inequality of the AB sublattice
potential competes [113] with the spin dependent Zeeman
term besides the SOC terms. Another approach [104] using
the method of invariants and group theory has constructed
an effective Hamiltonian for phosphorene and silicene with
strain, an electric field and an external magnetic field. This
work is a generalization of work adopted by Geissler [53] and
Li et al [114]. This method gives a proper justification of dif-
ferences observed in the band structure of graphene, silicene
and phosphorene. The formal analyses, which are not possible
in the framework of ab initio calculation, can be justified by
this approach. Moreover, features obtained from DFT band
structure calculations can be appropriately judged via this TB
Hamiltonian approach. In this sense, these theoretical predic-
tions can serve as a benchmark to understand the numerical
results involved in DFT calculations.
3.  Modification of electronic properties
3.1.  Chemical functionalization of silicene
Although theoretically, various aspects of pure silicene have
been explored, there are some compelling reasons for the grow-
ing interests in both the theoretical as well as the exper­imental
study of the chemical functionalization of silicene. Firstly and
exfoliation of calcium disilicide, like any other nanostructure
naturally leads to a functionalized sheet. Secondly, by adding
various suitable foreign atoms at various sites, one can con-
trol the electronic, optical and transport properties in contrast
to pristine silicene sheets. This may open up the possibility
for the fabrication of future nanodevices involving the exist-
ing Si technology. In other words, like graphene, the feasibility
of employing silicene in various nanoelectronic applications
depends critically on the suitable control of its electronic prop-
erties by chemical functionalization. To date, several general
types of functionalizations have been attempted for silicene:
hydrogenation, halogenation, by metals, organic groups, oxi-
dation, doping and the formation of 2D hybrids [115].
3.1.1. Monolayer.  It has been pointed out that silicene has
comparatively higher reactivity than graphene; function-
alization in silicene should significantly modify or tune its
Rep. Prog. Phys. 79 (2016) 126501
Figure 4.  (a) Fully brominated crystal structure of silicene (b) and its corresponding band structure. (Reproduced with permission from
[116]. Copyright (2012) by Springer.)
electronic, magnetic and optical properties for possible appli-
cation in nanoscale devices.
In view of future nanoelectronics, hydrogenation is a novel
method to tune the properties of silicene and germanene.
Motivated by the fact that fluorine atoms decorated on gra-
phene or CNT can induce magnetic properties, Zheng et  al
[116] employed first-principles calculations to investigate
the electronic structure and magnetic properties of 2D hex-
agonal silicene adsorbed with H and Br atoms. They noticed
that the fully saturated silicene exhibits nonmagnetic (NM)
semiconducting behavior, while half-saturation on only one
side with hydrogen or bromine results in the localized and
unpaired electrons of the unsaturated Si atoms, showing fer-
romagnetic (FM) semiconducting or half-metallic properties,
respectively. However, DFT calculations based on the gener-
alized gradient approximation (GGA) scheme indicate that
half H-silicene without substrates turns out to be an FM semi-
conductor having an indirect band gap of the order of 0.84 eV
[117] and 0.95 eV [118]. The origin of this bandgap lies in
the fact that the half-hydrogenation essentially breaks the
extended π-bonding network of silicene, leaving the electrons
in the unsaturated Si atoms localized and unpaired [118]. On
the other hand, the fully H-silicene silicane generates about a
2 eV indirect band gap by local density approximation (LDA)
calculations and becomes an insulator [312]. Instead of the
Perdew–Burke–Ernzerhof (PBE)-GGA functional, Wang et al
[119] used the Hyed–Scuseria–Ernzerhof (HSE06) functional
to demonstrate that one-sided semihydrogenated silicene and
germanene possessed direct band gaps of 1.74 eV and 1.32 eV
respectively, larger than predicted by PBE–GGA. Note that
this type of induced ferromagnetism does not require any dop-
ing, cutting or etching. Therefore, by applying an appropriate
hydrogenation ratio, the band structure of silicene can be tai-
lored to produce metallic, semiconducting, or insulating prop-
erties. Also, controlling the coverage of hydrogenation and the
geometry turns out to be the key to observe this predicted FM.
12
Review
Garcia et  al [311] have performed a systematic DFT–GGA
investigation of the group-IV elements extending up to Sn
and fluorinated graphene-like samples. Interestingly, fluori-
nated structures were found to be more energetically stable
than the corresponding hydrogenated structures. However, no
band gap opening was observed for the fluorinated Sn struc-
ture. This is quite contrary to fluorinated graphene, silicene,
and germanene (for comparison please see table  3 of [15]).
These results naturally open a door to widen the applications
of silicene-based devices and invite further investigations in
the optical as well as transport properties.
To check the collectiveness in the magnetic order, the
energy difference between FM and antiferromagnetic (AFM),
was found to be 0.068 eV, indicating eventually that the FM
order is the stable ground state. In the mean field level [120],
1
using the relation γkBTC = 2 (EAFM − EFM ) (γ being the struc-
tural dimension), one can compute the Curie temperature
(TC) as 300 K. Further, when silicene was fully brominated
on both sides, an NM semiconducting behavior was noticed
with a direct bandgap smaller than that of H-silicene [121]. In
­figure  4, we schematically show the fully brominated struc-
ture of silicene and its corresponding band structure. Besides,
the half brominated silicene is indeed AFM half-metal [116]
behaving as metal in one spin channel while in the other as
semiconducting with a gap of 1.73 eV. Therefore, the study
indicates that the electronic properties of silicene can be tuned,
and especially, the long range FM order at room temperature
is possible in the silicene sheets, which may open a new route
to design the silicon-based nanostructures in spintronics.
Recent calculations [122] have pointed out that the chem-
isorption of adatom species H, Li, F, Sc, Ti, V on the mono­
layer configurations of silicene and germanene have a distinct
effect on the electronic structure, yielding metallic or semi-
conducting dispersions depending on the adatom species and
configuration. The induced bandgap is an (in)direct Γ gap
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 5.  (a) Simulated structure of 4 × 4 silicene on Ag(1 1 1) substrate used in DFT. (b) Initial adsorption sites of oxygen adatoms on
silicene. (c) Calculated DOS of oxidized silicene with oxygen coverage of monolayer (ML). The inset represents an enlarged view of the
DOS near the Fermi level. (d) The energy-favored stable adsorption site after running MD for 7 ps. Si–O–Si bonds at bridge sites in the 44
silicene surfaces prefer to be formed by the oxygen adatoms. Red, yellow, and blue balls in (b) and (d) represent oxygen, silicon, and silver
atoms, respectively. (Reproduced by permission from Macmillan Publishers Ltd: [124], copyright (2014).)

ranging from 0.2–2.3 eV for both silicene and germanene.
In particular, the hollow configuration combined with vdW
bonded adatoms/physisorbed adatoms was suggestive to mini-
mize the orbital hybridization for avoiding the surface states
detrimental for device applications.
Interestingly, interfacing silicene with a gate dielectric
material is essential for any feasible voltage bias application,
but also to save it from possible destructive reactivity under
ambient conditions. The stability of FS silicene in O2 has been
explored via first principles calculations by Liu et  al [123].
Their computations have pointed out that silicene is indeed
unstable because the O2 molecule can be easily adsorbed
and dissociates into O atoms without overcoming any energy
barrier on pristine silicene. The dissociation process is an
exothermic one and is different from the graphene case.
Moreover, the calculated energy gain for one O2 molecule dis-
sociation and adsorption on the pristine silicene lies between
4.04–5.36 eV for all the simulated structures with different
adsorption sites. For the functionalization of silicene layers,
it is important to know the key role of electronic coupling in
the chemical reactivity between the silicene and the substrate.
For this purpose, hybridizations and the electronic structure
of (4 × 4) silicene on the Ag(1 1 1) surface was explored via
STM, ARPES and x-ray photon spectroscopy (XPS). It has
been observed by Xu et  al [124] that the binding energy
between the epitaxial silicene layer and the Ag(1 1 1) surface
is approximately 0.7 eV, which is comparatively smaller than
the binding energy for Si–O (between 4.0 and 12.0 eV) [125].
Therefore, the oxygen will naturally tend to bond firstly with
Si atoms in the silicene rather than with Ag atoms in the sub-
strate. Further, the energy necessary for oxygen adsorption
on Ag(1 1 1) is much higher than on the Si surface with DBs
(pz orbital), and therefore, the bare Ag(1 1 1) surface but not
the silver oxide appears in the fully oxidized silicene sample.
Moreover, due to the characteristic sp3 hybridization of Si,
energetically stable Si–O–Si bonds would be expected when
silicene is exposed to a high oxygen dose (see figure 5). It is
clear from figure 5(c) that the Ag 4d-state and the Si 3p-state
make the largest contributions to DOS at the Fermi level (EF).
These theoretical and exper­imental results [124] also indi-
cate that the silicene oxide layer could possibly detach from
the Ag(1 1 1) substrate and form quasi-FS NSs. Hence, it has
been proposed by analogy with graphene, that reducing these
quasi-FS NSs may offer a feasible way to obtain FS silicene
NSs (or reduced silicene oxide). It has been recently demon-
strated [126] through XPS and Raman study that aluminium
oxide (Al2O3) /Al/silicene/ Ag and Al2O3 /silicene/Ag hetero-
structures are chemically inert with respect to oxidation and

13
Rep. Prog. Phys. 79 (2016) 126501
Figure 6.  (a) Geometry structure of a silicane sheet from top view and side view used for DFT calculation. The dashed line indicates the
primitive unit cell. (b) Variation of the band gap and strain energy of silicane as a function of uniform tensile strain. (c) Band structure
of silicane under strain values of 0.0, 0.1, and 0.2 showing semiconductor to metal transition. (Reproduced with permission from [128].
Copyright (2013) by the Chinese Physics Society and IOP Publishing Ltd.)
thus can be used in situ characterization as well as for gated
device fabrication. Further, this type of encapsulation can be
inherently applied to any silicene configuration regardless of
the substrate. It is noteworthy that Ag is the most common
substrate for silicene due to the fact that the effective inter-
action between Ag and silicene judiciously stabilizes sp2
hybridization. There are, in fact, three important distinct char-
acteristics of this exotic Si/Ag surface [127]. Firstly, Si and Ag
have a phase separation with a comparatively low solubility of
Si in bulk Ag. Besides, due to the similar lattice constants of
Si and Ag, the formation of Si takes place on the top of the Ag
surface only without any appreciable Si diffusion. Apart from
this, the balanced homogeneous interaction between Si and
Ag controls the smallness of the local tension in the growth
process. However, despite being an excellent substrate, the Ag
substrate is known to degrade some properties of silicene.
Silicane, another popular derivative of silicene, undergoes
an indirect to direct gap transition under the application of
uniform small strain and a semiconductor to metal trans­
ition under a large strain [128]. Besides, the bandgap of sili-
cane decreases monotonically with the increase of strain. In
­figure 6, we show the variation of band gap and strain energy
along with the semiconductor to metal phase transition under
the application of external strain. Under uniaxial tensile strain,
14
Review
the different variations of the band gap of the silicene and sili-
cane structure with strain and chirality have been observed
[129]. It has also been pointed out in this study that the chi-
rality effect is more significant in the mechanical properties
of silicene than those of silicane. From the first principles
calculations on the variations of band structure by strains, it
has been envisaged [130] that both silicene and germanene
possess strain-induced self-doping behavior in the Dirac-like
electronic structures. This type of doping, in contrast to dop-
ing in graphene, does not require adsorbed atoms or molecules
in the NSs and the distance between the Dirac point and Fermi
level can be tailored by the magnitude of the strain. Besides,
the n-type/zero-band gap/p-type semiconducting behavior can
be switched by applying strains. DFT calculations by Liu et al
[131] have predicted that silicene keeps its semi-metallic char-
acter up to 7.5% tensile strain and beyond this strain, silicene
transforms into a metal. Recently, DFT  +  Green’s function
and (screened) Coulomb interaction (GW) (many body study)
formalism have been adopted [132] to study the electronic
and optical properties of silicane under uniform biaxial ten-
sile strain. The calculations have predicted that the bandgap
can be efficiently tuned in a broad range, and an indirect to
direct bandgap transition is observed under a strain of 2.74%.
Further, the semiconducting silicane can even be engineered
Rep. Prog. Phys. 79 (2016) 126501
Figure 7.  Band structure for bare and fully lithiated silicene obtained by using GGA. Fermi energy has been set to zero. (Reproduced with
permission from [312]. Copyright (2012) by the American Chemical Society.)
into a metal under a very large strain. The bandgap transitions
are attributed to the downward shift of the lowest CB at the
Γ-point as the strain increases. Moreover, the quasi-particle
bandgaps of silicane are sizable due to the weak dielectric
screening and the low dimension. Also, the optical absorp-
tion edge of the strained silicane significantly shifts towards a
low photon energy region and falls into the visible light range.
This feature makes strained silicane a promising candidate for
optoelectronic devices.
An ab initio study of atom adsorption and absorption of B,
N, Al and P atoms on silicene was used [133] to explore the
electronic and vibrational properties of the doped system. The
calculations clearly indicate all the final systems as metallic.
Besides, the adatoms are strongly bonded with silicene reveal-
ing different preferential adsorption sites for B or N adatoms
as compared to graphene. Further, the analysis of the vibra-
tional modes have pointed out that the adatoms and substitu-
ents slightly alter the phonon spectrum of silicene and several
adatom/substituent-induced characteristic branches appear,
which may be probed by Raman measurements. The stabili-
ties of B, N, Al and P adsorbed/substituted silicene layers,
even at high temperatures, were also confirmed. This study
has clearly indicated that silicene has a very reactive and func-
tionalizable surface suitable for novel nanoscale materials,
even at high enough temperatures. DFT investigations have
been employed [134] to find the appropriate nitric oxide (NO)
adsorption sites in a pristine Al and P doped silicene NS. The
study indicates that the substitution of P atoms on the silicene
NS can effectively enhance the adsorption of NO on the sheet,
thus validating it as a chemical sensor.
Like graphene, metals in a silicene sheet also can induce
various interesting properties [28]. It is illuminating to point
out that, except for alkali metals, metal adatoms in com-
parison to graphene bind strongly to silicene [28]. The first-
principles calculation of the electronic band structure of
lithiated silicene, known as silicel, have indicated [312] that
the silicene is transformed from a zerogap semiconductor to a
0.368 eV bandgap semiconductor upon complete lithiation. In
figure 7, we show schematic comparison of the band structure
of silicene and silicel under GGA. It is instructive to point out
that graphene after lithiation behaves as a metal [135], while
15
Review
silicene behaves as a semiconductor. Besides, graphene and
silicene have a zero-gap and linear dispersion at the K point;
however, silicel does not. It will be interesting to explore any
variation of optical properties with the doping concentration
of lithium atoms in a silicene network.
3D TM (Sc, Ti, V, Cr, Mn, Fe, Co, Ni) doped silicene can
be an intriguing system because of the manifestation of strong
magnetic moments, potential half-metallic property, and most
significantly, sizable topologically non-trivial gaps [113].
The numerical results strongly indicate that the TM-silicene
systems are strongly magnetic with considerably strong
bonding between TM and silicene. In figure 8, we show the
schematic (4 × 4) super cell TM doped silicene model and the
band structure of V-doped silicene under the GGA+Hubbard
U+SOC scheme. It can be clearly seen from the figure that
a gap is opened at the Fermi level. Further, a combined TB
model analysis and first principles Wannier interpolation
methods were adopted to show that the V doped silicene hosts
a stable QAHE which survives the strong correlation effect of
the adatom. In fact, this system can also be half-metallic if the
Fermi level is properly tailored. Moreover, with the help of
the TB model, the band structure of pristine silicene is probed
with the interplay between the effective spin dependent magn­
etic field M and the site-dependent staggered potential ∆. It is
to be noted that when the 3D TM is adsorbed on a particular
site or an external electric field is applied, then there arises an
induced inequality of AB sublattice potential (∆) which natu-
rally tries to compete with magnetization. In figure 9, we show
the evolution of this band gap at the K point in pristine silicene
with various values of M and ∆. It is interesting to point out
that when M = ∆ there always exists a degenerate point right
at the Fermi level (shown in figure 9(e)). However, in the limit
of M > ∆, the two spin subbands near the Fermi level cross
each other resulting in a circular Fermi surface (shown in
figure 9(f)). Finally, when M < ∆, the system is an insulating
state. Thus tuning M and ∆, one can enter the various phases
of pristine silicene necessary for QAHE observation.
Since nickel silicide is an important material for silicon
devices, it is natural to explore the modifications of the elec-
tronic band structure by Ni adatoms in silicene. The DFT based
first-principles calculations [136] have triggered that a planar
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 8.  (a) Lattice geometry of 3D TM doped silicene, super cell. (b) Side view of the doped structure with buckling. (c) Band structure
of V doped silicene under GGA+U+SOC scheme. (Reproduced from [113]. Copyright (2013) with permission from Elsevier.)

Figure 9.  Evolution of band structure around valley K. The evolution of band structure around valley K from the interplay between
exchange field M and staggered potential. (Reproduced from [113]. Copyright (2013) with permission from Elsevier.)

as well as a buckled sheet of Si is stabilized by Ni doping.
Although the planar sheets possess unstable phonon modes,
they exhibit better in-plane stiffness in comparison to buckled
ones. Most importantly, by doping with Ni, the electronic struc-
ture calcul­ations have established that the linear dispersion of
the bands at the Dirac point transforms to a parabolic (quad-
ratic) type. This may be due to the localized narrow d bands of
Ni. Besides, the presence of finite DOS at the Fermi level indi-
cates the enhanced metallicity in comparison with the pristine
sheets. Again, Fe and Co atoms having nearly the same size as
that of Ni atoms, the calculations yielded similar results as that
of Ni. The Fe and Co doped silicene sheets are metallic like Ni
ones. However, the electronic properties near the Fermi level
are not affected as, like Ni, the Fe and Co d-states lie deeper.
The band structure of silicene can be tuned into various
types, such as semimetals, semiconductors, and insulators, by
chemical functionalizations with oxygen, so called oxidation
[137, 138]. It has been clearly demonstrated by Du et al [139],
through STM and in situ Raman spectroscopy studies, that the
band gap of silicene monolayers grown on Ag(1 1 1) surfaces
can be tailored by oxygen adatoms from semimetallic to semi-
conducting. The order of the magnitude of the gap, however,
shows significant characteristic variation corresponding to the
different superstructures. Moreover, the gap is larger at oxy-
gen adatom sites and becomes smaller in the locations away
from the absorption sites. In comparison to graphene, oxygen
adatoms in silicene prefer to be accommodated at the surface
of silicene rather than the edge. This is most likely because the
DBs on edge Si atoms are passivated by the Ag(1 1 1) surface.
Huang et al have demonstrated [140] that chemically func-
tionalized epitaxial silicene can undergo a spontaneous struc-
tural transition due to the preference of sp3 hybridization of

16
Rep. Prog. Phys. 79 (2016) 126501
Figure 10.  The electronic band structure for epitaxial SiFx and SiOx : (a) Si12F4 (b) Si6F3 (c) Si12F11 (d) Si12O4. Here, the positions of
CBM and VBM are highlighted by a red dot. The Fermi level has been set equal to zero. (e) The top and side view of Si8P4 (blue and pink
represent respectively Si and P). (f) the calculated band structure of Si8P4. (Reproduced with permission from [140]. Copyright (2013) by
the American Physical Society.)
silicon leading to continuously tunable band gaps. Theoretical
predictions by this group also suggest that metastable silicene
can also be used as an important host material to produce novel
functional materials via substitutional doping. In figure 10, we
schematically show the band structure of various alloys of
these metastable silicene. As an example, it has been shown
that Si6F3 behaves as an n-type semiconductor with an indirect
band gap of 0.51 eV. In a similar fashion, the calculations have
yielded that Si12F11 can also be considered as a silicon fluoride
with an F vacancy behaving as a p-type semiconductor with a
direct band gap of 2.17 eV. Finally, the ordered structure Si8P4
(shown in figure 10(e)) is found to be a direct gap semiconduc-
tor with a band gap (shown in figure 10(f)) of 1.53 eV. Because
of this value of the band gap, Si8P4 could be a strong prom-
ising candidate for thin-film solar cell absorbers beyond bulk
Si. In figure 11, we also depict that the variation of band gaps
of homogeneous SiFx (growth temperature 875 K) and SiHx
(growth temperature 795 K) could be continually tuned from
0–1.59 eV and 0–2.92 eV respectively. An extensive summary
of band gaps of functionalized silicene NSs along with its pos-
sible magnetic nature has been presented in [8].
The interaction of silicene with various semiconduct-
ing dichalcogenide substrates, namely MoX2 [98, 141] with
X  =  S, Se, Te has been significantly effective to control the
17
Review
electronic properties of these silicene heterolayer structures.
For example, it has been demonstrated [141] that, like FS
silicene, silicene on MoTe2 is a gapless semiconductor. ZnS
can be regarded as another non-metallic template [98] for the
growth of silicene.
The functionalization of FS silicene with various small
organic molecules, such as benzene, methane, toluene [142,
143] and phenyl groups [144, 145] has been theoretically car-
ried out. The calculations have indicated that the structures
thus formed are indeed stable and the electronic properties of
these systems are significantly modified by exchanging the
functionalizing molecules. The oxygen free, phenyl-modified
organosilicon NSs (Si6HxPh6−x) with atomic thickness have
been synthesized [146] and the IR spectra, nuclear magnetic
resonance study along with x-ray absorption near-edge struc-
ture analysis confirmed the formation of this NS structure. DFT
calculations of the organic functionalization of H-silicene with
acetylene, ethylene and styrene have been performed recently
by Pereda et al [143] and the results on the chemical reaction
have indicated that the growth of styrene on (H-silicene) [111]
is possible. For acetylene, since the total number is even, the
partial density of states (PDOS) remains identical for up and
down electrons. However, it is observed that the intermedi-
ate state in both cases is quite stable in silicene, and also the
Rep. Prog. Phys. 79 (2016) 126501
Figure 11.  The calculated band gaps of double-sided SiFx and SiHx
alloys as a function of F or H concentration (x). (Reproduced with
permission from [140]. Copyright (2013) by the American Physical
Society.)
abstraction barrier is much smaller than in Si [1 1 1]. In recent
DFT calculations taking into account the vdW interactions,
Stephan et al [147] have shown clearly that the organic ben-
zene molecule can be chemisorbed through a cyclo addition
reaction on a silicene layer deposited on Ag(1 1 1). Moreover,
in addition to the formation of two covalent Si–C bonds, the
benzene molecule adopts a butterfly configuration. Polycyclic
aromatic hydrocarbon, such as naphthyl or anthracyl groups,
can be attached to appropriate positions to generate new
derivatives of stable silicene structures with a direct band gap
[148]. In such a situation, MD and ab initio calculations have
indicated that the band gap can be tuned from 1.25–1.29 eV
for bilayer structures. It is demonstrated clearly that with the
increase of the length of polycyclic aromatic hydrocarbon
or the thickness of silicene, the band gap is reduced. Thus,
by changing different organic functional groups or the thick-
ness of the silicene opens a viable route to use this material as
electronic devices and nanosensors. The effects of hydroxyl
(OH) group substitution have been explored [149] on phenyl
modified silicene to show that para-substitution is the most
stable one via density functional tight-binding (DFTB) and
ab initio MD methods. A direct band gap of 1.93 eV has been
predicted, and this is in contrast to other alkoxylated and ami-
nated silicene having an indirect one [150].
3.1.2. Bilayer.  Like graphene, the stacking order and inter-
layer may play an important key role in tailoring the prop-
erties of multilayered silicene. Even the covalent orbitals
between two layers play a substituted role in chemical dop-
ing. Thus, a vertically applied external electric field to bilayer
silicene (BLS) in contrast to bilayer graphene can effectively
control surface doping as well as electrical gating. This may
indeed satisfy the requirement of high on/off ratios in FET
applications. Besides, BLS possesses higher stability due to
interlayer interaction and a sizeable band gap suitable for
device applications. Further, BLS shows different possible
structures depending on stacking style [151], indicating a pos-
sibility of the emergence of intriguing physical properties.
Buckling is responsible for such complex and rich variation
of the structure of BLS [152]. In contrast to bilayer graphene,
18
Review
Table 4.  Some important parameters of BLS.
Parameters Monolayer AA layer AB layer
Lattice constant a (Å) 3.825–3.83 3.817 3.806
Interlayer spacing d1 (Å) ... 2.429 2.481
Buckling parameter ∆0 (Å) 0.438–0.44 0.647 0.659
Note: Reproduced with permission from [155]. Copyright (2014) by the AIP
Publishing LLC.
however, here the Dirac cone in pristine silicene is destroyed
in BLS due to strong interactions between two silicene lay-
ers. Recently, theoretical computations by Liu et al [153] have
established that intercalation of alkali metals (such as Li, Na,
K and Rb) can effectively weaken such interlayer interaction
and thus stabilizes the system. In particular, K intercalation
can indeed recover the outstanding electronic properties of FS
monolayer silicene by forming a double-degenerated Dirac
cone with a small band gap of 0.27 eV below the Fermi level.
Moreover, intercalation of K+ cations in BLS (K+ Si4) results
in a semiconductor having a moderate band gap of 0.43 eV.
Besides, the computed effective masses of the hole and elec-
tron for this system are  −0.174me and 0.215me (where me is
the free electron mass) indicating the high carrier mobility
particularly suitable for microelectronic devices.
An ab initio DFT, including vdW interaction for the for-
mation of a silicene bilayer on top of the Ag(1 1 1) surface,
has been recently proposed by Pflugradt et  al [154]. The
calculations have revealed that, in comparison to monolayer
silicene,(2 3 × 2 3 ) R30 translational symmetry is stable
on ( 19 × 19 ) R23.4 Ag substrate. The BLS system, how-
ever, shows an AA-stacking, with each silicene layer decay-
ing into a lower buckled system. The properties obtained
from the optimized atomic geometry of the adsorbate sys-
tem are in good agreement with the experimental data of the
STM images, low energy electron diffraction (LEED) spots,
and ARPES measurements. The band structure of the com-
plete adsorbate system shows conical linear bands near the
Fermi level with an apex position  −0.22 eV below the Fermi
level and a Fermi velocity of 0.3 × 106 m s−1 consistent with
ARPES data. It should be noted that the Fermi velocity of the
monolayer system is much larger than that of the BL system.
These quantitative values can be explained by hybridized Ag
states and not as Dirac cones derived from Si π states.
DFT calculations [155] have been adopted to investigate
the formation and electronic properties of BLS and hydro-
genated bilayer silicene (HBLS). The calculations dem-
onstrated clearly that BLS has a stable structure with AB
stacking and preserves the linear energy dispersions near the
K and K’ points in the hexagonal BZ. The Fermi velocity
of BLS is 0.65 × 106 m s−1 slightly less compared to mono­
layer silicene (1.15 × 106 m s−1). In table  4, we show the
important parameters required for the optimization of BLS.
There are four possible configurations of HBLS based on
the symmetry. The BLS with a semi-hydrogenated one-layer
shows an indirect band gap of 0.12 eV with an FM ground
state due to the unpaired 3p electrons, while the BLS with a
semi-hydrogenated double-layer is also an indirect band gap
Rep. Prog. Phys. 79 (2016) 126501
Figure 12.  The relaxed structures of BLS (a) top and (b) side views, (c) SOC band gap curve as a function of interlayer distances of BLS,
(d) schematic evolution of the band gap (red: bilayer silicene; blue: graphene-like BLS) with voltages. (Reproduced from [159] with
permission of The Royal Society of Chemistry.)
semiconductor with an energy gap of 1.28 eV, but exhibits an
NM ground state. Usually, the magnetism of a system origi-
nates from the interplay of d and f electrons. However, in this
case, DOS calcul­ations have indicated that the FM of HBLS
with 1-H configuration is caused by localized and unpaired
3p electrons. Since all the Si atoms are saturated to form the
sp3 hybridization, the 2-H configuration BLS does not carry
any magnetic moment leading to an NM ground state. In this
sense, BLS in a 2-H configuration is similar to the bilayer
graphene because the C or Si atom in both materials pos-
sesses the same hybridization [156].
Because of finite non-zero buckling, unlike graphene
which has only AB (Bernal) stacking, there are wide varie-
ties of morphological BLS structures due to possible inter-
layer covalent bonds. By controlling the interlayer slide of
the BLS sheet, it is possible to modify the electronic prop-
erties to achieve electronic transitions between metals, semi-
metal and semiconducting properties in various meta-stable
configurations of BLS [157]. Three possible bilayers of sili-
cane (AA-chair-like, AB-chair-like, AA-boat-like) form after
hydrogenation, showing a transition [158] from semi-metal to
an indirect semiconductor material.
In the case of BLS, two possible important stackings,
known as AA and AB, possess same buckling parameters
∆0 = 0.68 Å but interlayer distance between two layers are
2.49 Å and 2.51 Å for AA and AB stacked respectively. Mohan
et al [23] have employed first principles DFT calcul­ation to
compare the electronic and optical properties of bilayer and
monolayer buckled silicene under an external vertical elec-
tric field. The electronic band structure of AB-stacked bilayer
buckled silicene at zero field indicates two types of cones
meeting with each other. The numerical results have also
yielded that BLS is an indirect gap semi-conductor with an
19
Review
electric field induced bandgap of 60 meV and 67 meV respec-
tively for AB and AA-stacked BLS. Further, the inter-band
transitions show blue-shift in the energy of electrically gated
monolayers and both AA and AB-stacked BLS.
Motivated by the intriguing features of monolayer silicene
and bilayer graphene, Liu et al [159] considered the evolution
of the electronic band structure of Bernal-stacked (AB) BLS
(shown in figures 12(a) and (b)) with 50% sp3 and 50% sp 2 /sp3
mixing hybridization of silicon atoms under a vertical field.
The stability of the structure was checked through the local
unique minimum in the total energy and real values of the
phonon (optical as well as acoustical) frequencies. The band
structure computation has revealed that the valence (π) and
→
conduction (π∗) bands cross linearly at the K point and another
→
low-symmetry point between K and Γ points in the BZ and
near the Fermi energy level. This indicates that BLS behaves
like a metal. In figure 12(c), we schematically show the vari-
ation of the SOC energy band gap as a function of inter layer
separation between two layers in these two cases. It is noted
that the SOC energy band gap in BLS is larger than in mono­
layer silicene (1.55 meV) predicted by Liu et  al [84]. The
variation of the bandgap as a function of voltages for bilayer
silicene and graphene is compared in figure 12(d). It is clearly
observed that a continuously and widely tunable band gap
with the maximum value of 1.13 eV, which is largely wider
than that (0.25 eV) of bilayer graphene, can be generated in
such BLS.
The first-principles calculations armed with the cluster-
expansion approach have been adopted by Huang et al [160]
to explore the opto-electronic properties of HBLS. The study
is motivated by the fact that intrinsic BLS is a strongly indi-
rect-gap semiconductor. When the gap differences between
the indirect band gap and minimum direct band gap are less
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 13.  Variation of the calculated band gaps of (a) single-sided SiHx and (b) double-sided SiHx ground states as a function of
hydrogen concentration. In panel (b), a sketch of light spectrum is shown to aid visualization of the size of the band gap. (c) Comparison of
theoretical optical absorbance spectra of Si28H6, Si24H6, Si16H4 , and Si12H4 . The reference air-mass 1.5-solar spectral irradiance is plotted
in yellow. (Reproduced with permission from [160]. Copyright (2014) by the American Physical Society.)

than 0.1 eV, then it is known as a quasi-direct gap semicon-
ductor. The calculations have indicated that at low hydrogen
concentrations, four SiHx ground states (energy gap is given
in brackets), i.e. Si28H6 (1.01 eV), Si24H6 (1.30 eV), Si16H4
(1.52 eV), and Si12H4 (1.46 eV), behave as dipole-allowed
direct (or quasi-direct) band-gap semiconductors with prom-
ising gaps in the range of 1–1.5 eV, which are suitable for
solar Si-based photovoltaic (PV) applications. At high enough
hydrogen concentrations, there exist three well-ordered
double-sided HBLS structures having direct (or quasidirect)
band gaps within the color range of red, green, and blue. In
­figures 13(a) and (b), we show schematically the variation of
the band gap of single sided SiHx and double sided SiHx with
hydrogen concentration. While in figure 13(c), the absorbance
spectra of certain SiHx are compared with the solar one. In
particular, the carrier effective mass (both electron as well as
hole) computed from the band structure of Si12H4 is very small
(about 0.16me and 0.09me) indicating a high carrier mobility
correctly suitable for a good candidate as high efficiency solar
cells. Thus, simply controlling the hydrogen concentrations,
BLS can be potentially regarded as a new class of silicon-
based solar absorbers as well as white LEDs.
Hydrogen is generally regarded to be one of the cleanest
renewable energies due to the fact that it does not produce
pollutants or greenhouse gases. It is desirable to find suita-
ble materials for storing hydrogen safely and economically.
Neither the chemisorption of hydrogen in the form of Si–H
nor physisorption of hydrogen molecules on silicene is effec-
tive for the relevant order of magnitude of the binding energy.
In this situation, first principles calculations have been under-
taken by Song et  al [161] to study the effects of the exter-
nal electric field on the adsorption– desorption of H2 on a
Ca-decorated silicene system (Ca-silicene). The study [161]
has indicated that H2 can be adsorbed on Ca-silicene with
an average binding energy of 0.19 eV per H2. Because of the
enhancement of the charge transfer between H2 molecules and

20
Rep. Prog. Phys. 79 (2016) 126501
the Ca-silicene system, the external electric field can be fruit-
fully utilized as a switch to control the entire adsorption and
desorption in the hydrogen storage systems.
The structural and electronic properties of ultrathin double
layer (DL) Si with and without hydrogenation or substitutional
doping have been investigated by ab initio DFT at a GGA
level [162]. The band structure along with DOS shows that
DL-Si with DBs is indeed metallic; however without DBs, the
2D DL-Si shows a semi-conducting nature. Hydrogenation
and substitutional P doping induce an indirect band gap of
1.2 eV and 1.5 eV, respectively. It is worth pointing out that
doping P atoms into bulk C-Si generally transforms it into an
n type semiconductor. However, imperfect substitution of P in
DL-Si induces a deficiency of electrons compared to perfect
substitution (DL-SiP). Thus, an unreplaced Si atom in such an
imperfect DL-SiP acts like a B or Al impurity in C-Si, result-
ing in a p type semiconductor.
Recently, Padilha and Pontes [163] have theoretically
investigated the structural, electronic, and transport properties
of BLS. Because of the presence of large numbers of degrees
of freedom in the buckled structure of the silicene, its bilayer
structure can present several possible stacking configura-
tions. They have shown that the lowest energy configuration
becomes planar by losing its buckled structure since there is
an energy gain. Moreover, the BLS on this planar configura-
tion is a metal. The transmission coefficient turns out to be
highly dependent on the structure, and some structures also
show highly anisotropic behavior of the current as a function
of the direction of the applied bias. Thus, it remains as a chal-
lenge to the experimentalists to prepare such a BL system to
verify whether their intrinsic properties depend on the stack-
ing order or not.
Multilayer silicene, the silicon analogue of multilayer gra-
phene grown on Ag(1 1 1) surfaces, exhibits a cone-like dis-
persion at the BZ center, providing a clear signature of the
presence of gapless Dirac fermions from LEED and ARPES
measurements [164]. This is in contrast to a single monolayer
where there is a gap.
DFT calculation by Spencer et  al [165] have studied the
properties of Si NSs as a function of thickness. They have
indicated that the properties of the NS tend to those of the
bulk when the sheet is 1.42 nm thick. In particular, NSs hav-
ing more than two layers, a formation of Si(1 1 1)-2 × 1 recon-
struction with different orientation of π chain structures is
shown to modify the band gap.
3.1.3. Nanoribbons.  Because of the presence of quantum and
edge effects, SiNRs exhibit some intriguing physical proper-
ties in contrast to those of silicene, in particular relating to
width, sp2 like hybridization [166] and edge dependence. Gra-
phene nanoribbons (GNRs) exhibit important electronic prop-
erties based on the edge geometry and the width. For example,
in zigzag GNRs, the flat bands localized at the edge emerge.
In this sense, SiNRs are one of the few ideal systems to study
the bulk-edge correspondence. Again, the presence of edge
DBs requires hydrogenation for the stability of the structure.
Like GNRs, the main interest in SiNRs is to verify whether
there is an opening of the band gap and the magnetic nature is
21
Review
modified due to different types of shapes of the edges. SiNRs
also have potential applications in nanodevices, such as FET.
Nanoribbons were formally fabricated before the planar or
buckled sheet and were grown on the Ag (1 1 0) and Au(1 1 0)
surface [167]. Nanoribbons contain an array of uniform single
ribbons typically 1.6 nm in width. Evidence of Dirac cones
of SiNR on Ag(1 1 0) was established from ARPES measure-
ments [167]. In this case, the growth of this 1D honeycomb
material is mediated by the anisotropic Ag substrate.
Depending on the different shapes of the edges, the FS
SiNRs, like GNRs, can be classified into two categories-
ASiNR and zigzag silicene nanoribbons (ZSiNR). In the case
of the electronic structure of ASiNRs, the band gap oscil-
lates with a period of three when the ribbon width increases
[168, 169]. In fact, like zigzag GNR (ZGNR), the band-
gap of ZSiNRs decreases [169] monotonically as the width
increases. Moreover, the ZSiNRs possess a stable AFM con-
figuration, and the band structure can be tuned to a half-metal-
lic character under an external transverse electric field [169].
Furthermore, like ZGNRs, the pristine ZSiNRs also show a
symmetry-dependent transport property [170]. ZSiNRs can be
further classified by the number of Si atoms along the width
of the ribbon. Considering the symmetry-dependent proper-
ties of ZSiNR, we can choose the ZSiNRs with odd as well as
even widths of 5 and 6, which are indicated as 5ZSiNR and
6ZSiNR, respectively.
In contrast to armchair graphene nanoribbons (AGNRs),
silicane ribbons do not suffer from aromatic dependence of
the band gap. The theoretical calculations have predicted
[171] a direct and an indirect gap for ZSiNRs and ASiNRs,
respectively, and the band gap shows no aromaticity with rib-
bon width for either the ASiNRs or the ZSiNRs. Moreover,
the mobility in zigzag-edge ribbons is found to be approxi-
mately 20 times higher than in armchair-edge ribbons. DFT
calculations by Li et  al [172] have indicated that, although
the bare edges of zigzag silicane NRs can induce magnetic
moments, the passivated edges do not cause any magnetism.
The first principles calculations [169] have clearly demon-
strated that ASiNRs are NM in nature but could be metals or
semiconductors while ZSiNR possesses a semiconducting
AFM ground state. These results are the same as found in
graphene. However, ZSiNRs display spin degeneracy in the
AFM state, which naturally limits their application in spin-
tronic devices. The spin degeneracy, however, can be broken
by an electric field, defects, doping and edge modifications.
The asymmetry edge hydrogenation results in two edges with
different hybridizations sp2 and sp3. This can invariably give
rise to diverse magnetic properties in the SiNRs. Recently,
Zhang et al [173] have employed the nonequilibrium Green’s
function method and the spin-polarized DFT, to compute the
spin-dependent electronic transport properties of ZSiNRs with
asymmetric edge hydrogenation. These model calcul­ations
[173] on H2-5ZSiNR-H and H2-6ZSiNR-H devices have
shown that these devices have perfect spin filtering effects
with nearly 100% spin polarization and rectifying behavior.
The blocking of the spin-up and spin-down electrons also
indicates the emergence of giant magnetoresistance (GMR)
in such systems. Besides the rectifying behavior, GMR found
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 14.  Structures of (a) christmas-tree silicene nanoribbon (CSiNR) and (b) tree-saw silicene nanoribbon (TSiNR). Here, (n1, n2)
denotes the size of the structures, and the unit cells are marked by the gray rectangle lines. The applied external field (Ext) is indicated by
the downward green arrow CSiNR. (c) Variation of the energy gap of C(5, 4) and T(5, 3) as a function of Eext, and the inset shows the gap
of C(5, 4) near Eext = 0. (Reproduced from [174] with permission of The Royal Society of Chemistry.)

in the devices can trigger ZSiNRs, a promising candidate for
spintronic applications.
In recent years, sawtooth silicene nanoribbons (SSiNRs)
have been explored for their potential applications in spin-
tronics. There are two types of SSiNRs, one is known as
Christmas-tree silicene nanoribbons (CSiNRs) while the
other one as tree-saw silicene nanoribbons (TSiNRs). Both
are termed as SSiNRs since their edges resemble sawteeth as
shown in figure 14. In fact, the DFT calculations [174] have
indicated that SSiNRs are more stable than ZSiNRs. Just like
CNTs [175], here also we have to use two integers (n1, n2 ) to
label the size of the primitive cell used for numerical com-
putation. For CSiNRs, the two integers are the numbers of
hexagonal rings along the n1 and n2 directions. However, for
TSiNRs, n1 is the number of continuous zigzag chains while
n2 refers to the number of hexagonal rings along the n2 direc-
tion, as shown in figure  14. The computations have yielded
[174] that there exists an intrinsic energy gap of 0.25 eV and
0.19 eV, respectively for C(5,4) and T(5,3). In figure  14(c),
we schematically depict the tuning of the energy gap with the
applied external electric field. These features eventually point
out that the SSiNRs are spin semiconductors. Further analysis
has indicated that SSiNRs are spin-semiconductors with an
FM ground state. The spin-semiconducting feature originates
from the edge states.
DFT calculations have recently predicted [176] the poten-
tial application of SiNRs as CO nanosensors with molecular
level resolutions. In particular, this type of quantum conduc-
tion is detectably modified due to weak chemisorption of a
single CO molecule on a pristine SiNR. In fact, out of the
several molecules that were considered (CO, CO2, O2, N2, and
H2O), CO, O2, and H2O cause the most significant changes
in conductance, and naturally are predicted to be detectable.
As noted previously, the hydrogenated and fluorinated
silicene are known as H-silicane and F-silicane, respectively.
Out of all the possible configurations, the chair-like configu-
rations of H-silicane and F-silicane need to be specially men-
tioned because of their characteristic electronic features, as
stated below. The zigzag H-silicane NR with n zigzag chains
is known as H-nZSNR, while the armchair H-silicane NR
with n dimer lines is known as H-nASNR. The same defi-
nitions are followed also for the F-silicane NRs. Extensive
calculations of the electronic structure, including the Gibbs
energy, have been attempted by Fang et al [177]. Their com-
putations have yielded the band gaps for F-10ZSNR and
F-17ZSNR as 0.979 eV and 1.025 eV, respectively, which are

22
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 15.  Band structures of (a) H-4ZSNR and (b) H-17ASNR indicating the presence of direct and indirect band gap respectively.
(c) Schematic variation of the band gap of zigzag (4 ⩽ n ⩽ 16) and armchair (8 ⩽ n ⩽ 20) silicane NRs as a function of NR width. The
energy gap levels of H-silicane and F-silicane sheets are denoted by black and blue dashed lines, respectively. The inset shows the value
of E varying with the width of H-ZSNRs. (d) Variation of the band gap (estimated from the PBE functional) of H-10ZSNR, H-16ZSNR,
H-17ASNR, F-10ZSNR, F-16ZSNR, and F-17ASNR as a function of the electric field. (Reproduced with permission from [177]. Copyright
(2014) by IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.)

about half of that of H-10ZSNR. This clearly indicates that,
apart from hydrogenation, fluorination is another effective
avenue to tune the band gap of SiNRs. In figures 15(a) and (b),
the band structure of H-4ZSNR and H-17ASNR is shown to
indicate the nature of the bandgap. It is interesting to point out
that H-ZSNRs exhibit direct band gaps, while the H-ASNRs
remain as indirect band gap materials, just like the H-silicane
sheet. The calculated band gaps for H-4ZSNR and H-17ASNR
are found to be 2.526 eV, 2.348 eV, and 2.410 eV, respectively,
which seem to be slightly larger than that of the H-silicane
sheet due to the quantum confinement effect. Notice also
that for H-4ZSNR, the valence band maxima (VBM) and the
conduction band minima (CBM) are all located at the same
Γ point, which is completely different from the indirect band
gap of the H-silicane sheet. This emergence of a direct band
gap in H-ZSNRs can be ascribed to the BZ folding. In
­figure 15(c), we show the variation of the bandgap of all the
NRs with the NR width. It is evident from the figure that for sil-
icane NRs, the band gap decreases as the NR width increases,
while the armchair NRs possess a slightly larger bandgap than
the zigzag NRs. The computations also have indicated that
23
the band gaps of F-silicane NRs become about half of those
of H-silicane NRs. Further, in the inset of figure  15(c), ∆E
(defined as the energy difference between the energy of the
conduction band bottom at the X point and the energy of the
CBM at the Γ point as shown in figure 15(a)) also decreases
with increasing NR width. In particular, ∆E is 0.433 eV for
H-4ZSNR and changes to 0.047 eV for H-16ZSNR, show-
ing an obvious size effect. In figure 15(d), the variation of all
types of silicane NRs are explored as a function of the external
electric field. It is observed that the band gap of all silicane
NRs decreases with the increase of the strength of the electric
field, and reaches almost zero at some threshold electric fields.
Moreover, the wider the NR is, the smaller the threshold elec-
tric field. For NRs of a similar width, the threshold electric
field for F-ZSNR is seen to be about half of that for H-ZSNR.
Besides, the armchair NRs possess a larger threshold electric
field than the zigzag NRs. Undoubtedly, these electronic prop-
erties of silicane NRs will open up the possibility for their use
in nanodevices. Further study of the combinations of ZSiNRs
and A-SiNR is required to understand in detail the optical
properties for possible use in optoelectronic nano devices.
Rep. Prog. Phys. 79 (2016) 126501
Figure 16.  (a) The schematic structural model of ASiNR(7, 3), in which various substituted sites are indicated. (b) The formation energy
per impurity for N or B-doped ASiNR(7, 3) at the S0 and S0/S4 configurations, respectively. (Reproduced from [178] with permission of The
Royal Society of Chemistry.)
The electronic and magnetic properties of SiNRs doped by
a B/N pair have been investigated extensively with many pos-
sible structures through first-principles calculation [178, 179].
It has been concluded that with an isolated N or B impurity,
the states are localized [178] while all the B/N pairs intro-
duced states are rather extended [179]. It has been noticed
that the B/N pair tends to be doped at the edges of SiNRs.
Even the B/N pair doping in ASiNR is easier to carry out than
unbounded B/N pair doping in SiNRs. Further study indicates
that in contrast to the metallic states induced by the singly
substituted N or B atoms at the edges in ASiNRs, the B/N
bonded pair doping results in a semiconducting character
with the adjustable energy gap of ASiNR depending critically
on the B/N pair doping site in ASiNR. In figure 16 we have
depicted the structural model of ASiNR(7, 3) for various sub-
stituted sites and also the formation energy per impurity N
or B atoms. Here the first number within the parenthesis of
ASiNR(7, 3) is the number of the dimer line while the second
one is the number of unit cells. For ZSiNRs, the introduction
of a B/N pair induces a transition from NM to spin polarized
states. In figure  17 we have illustrated the structural model
of the ZSiNR(8, 4) in which various substitutional B/N pairs
are indicated. The band structures of AFM and FM states for
pristine ZSiNR(6, 4) are also presented. Significantly, when
the B/N pair is located in the edge or subedge sites, the amaz-
ing half-metal and spin gapless semiconductor with 100% spin
polarized currents around the Fermi level has been found.
These results may open an avenue for designing spintronic
devices, as there is a significant control over spins as well as
band structure in such nanoribbon systems.
Apart from B and N doping in SiNRs, recently, Al and P
doping were adopted on different sites [180] in even width
number SiNRs, such as in 6-ZSiNRs, to extract the information
regarding the modification of the band-structure properties. It
has been noticed [180] that when an Al atom replaces a single
Si one, on sites 2, 4, or 5 of a supercell of three primitive cells,
24
Review
the 6-ZSiNRs show a half-metallic behavior along with 100%
spin polarization. Further, the magnetic moment on the edge
is considerably suppressed when either an Al, P or B atom is
doped on the edge or near-edge sites. Besides, when a line of
six Al atoms replaces one of the Si atoms along the ribbon’s
width, the spin resolution of the band structure is suppressed.
In this case, since the system maintains the mirror symmetry
along the central line of the ribbon as in the pristine case, the
bands are not spin resolved. Therefore, although in general a
metallic or semiconducting behavior is expected, depending
on the positions of the replaced atoms by Al or P, a gapless
spin semiconductor behavior is also possible. This eventually
indicates that 6-ZSiNRs, doped by Al or P on different sites,
can provide various designs of spintronic devices. Recently,
from the quantum-mechanical Landauer–Büttiker approach,
strong evidence for the development of mobility gaps due to
the emergence of localized states has been provided [181] in
computing the conductivities in SiNRs due to Al, B, N and P
doping.
Defects are almost inevitable, either during the fabrica-
tion or in the growth process, and their existence strongly
influences [182] thermodynamic as well as (opto)electronic
properties of any 2D materials. In fact, a detailed study involv-
ing three types of defects—vacancy clusters, extended line
defects, and di-adatoms in a silicene monolayer—indicates
that they can control the magnetic moment and open up the
band gap in the silicene system. The first-principles calcul­
ations have shown that the band gap and magnetic state of any
armchair or zigzag nanoribbons of graphene can be modified
by a single or multiple vacancies (void) [183]. The effects of
these defects naturally depend critically on their symmetry,
repeating periodicity, and their relative positions with respect
to the edge of the nanoribbon. For example, the structural and
electronic properties of the ASiNR can be modified [184] by
the periodic monovacancy (1V) or divacancy (2V). Studies
on H-terminated 13-ASiNR have indicated that either a 1V
Rep. Prog. Phys. 79 (2016) 126501
Figure 17.  (a) The schematic structural model of the ZSiNR(8, 4) in which various substitutional B/N pairs are indicated. (b) The band
structure of AFM, and (c) the band structure of FM states for pristine ZSiNR(6, 4) are also presented. (Reproduced with permission from
[179]. Copyright (2013) by American Chemical Society.)
or a parallel-oriented 2V can change a direct semiconduc-
tor ASiNR to an indirect one, while a slanting oriented 2V
changes it to a metallic one. Moreover, the effects of a 2V on
the structural and electronic properties of the ASiNR, how-
ever, depend essentially on the orientation of the two removed
Si atoms. Besides, neither a 1V nor a 2V can make the ASiNR
possess a magnetic character having a non-zero magnetic
moment.
The presence of the Stone–Wales (SW) defect can signifi-
cantly alter [185, 186] the electronic and magnetic proper-
ties of SiNR. A SW defect can be created by rotating a Si–Si
bond 90, which can be experimentally formed during the
growth process under electron irradiation. Interestingly, the
SW defect was found to be the most stable [187] at the edge
of the ZSiNR. Moreover, the study [185, 186] has revealed
25
Review
→
that silicene sheets exhibit a direct band gap at the K point.
The study is also important from the point of view in contrast
to infinite silicene sheets, these defects can relax the strain
in ZSiNR. On the otherhand, the presence of an SW defect
results in the reconstruction of the edge atoms in SiNR with
an effective re-distribution of valence electrons. Therefore,
it is expected to give some information regarding the defect
position dependent magnetic properties of L-SiNR, where L
denotes the number of primitive cells along the ribbon length
direction. The first-principles study involving two types of SW
defects in L-SiNR has indicated [187] that the SW defect can
transform the ZSiNR from semiconducting to half-metallic
and eventually to semiconducting. In figure 18, we schemati-
cally sketch the variation of the magnetic moment and spin
band gaps of 5-ZSiNR with the defect positions. The defects
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 18.  (a) Schematic plot of magnetic moments of defective 5-ZSiNRs versus the defect positions and (b) band gaps of defective
5-ZSiNRs versus the defect positions (note that the metallic spin channel is represented here as zero while the black dotted line corresponds
to the band gap of the perfect 5-ZSiNR). (c) Summary of electronic properties of defective ZSiNRs with various defect positions. The black
dashed lines are the dividing lines between the different electronic properties. (Reproduced with permission from [187]. Copyright (2015)
by AIP Publishing LLC.)

were allowed to move from the edge to the center. It is observed
from figure 18(a) that the total magnetic moment is maximum
at n  =  1, then gradually decreasing, reaches to the minimum
value of zero at n  =  5. Figure 18(b) indicates the reduction of
the band gaps of defective 5-ZSiNR in compariso­n to pris-
tine. Finally, figure  18(c) classifies the modification of the
electronic properties of defective ZSiNRs with various defect
positions. Besides, the electronic and magnetic properties of
defective ZSiNRs can also be modulated by defect concentra-
tion, or defect orientation. Moreover, when L is greater than
7, for any n, the defective ZSiNR sustains the semiconduct-
ing nature. Xu et al [188] have established that by applying a
vertical magnetic field, ZSiNR can switch between anti-FM
and FM coupled states and a large magnetoresistance persists
between the semiconducting anti-FM state and the metallic
FM state. It will be worth pursuing the optical properties of
these defected SiNRs as a function of L.
The FETs based on semiconductor ASiNRs have been
investigated by Li et al [73] using ab initio quantum transport
methods and the calculations have revealed that the intrinsic
ASiNR-based FETs exhibit a high performance bipolar gate
effect with an Ion /Ioff ratio of over 106. A spin-polarized current
in a two-terminal ZSiNR can be induced, even in the absence
of Rashba SOC, with the help of a weak local exchange field
[106]. In such a case, when a weak local exchange field par-
allel to the surface of silicene is applied on one of the edges
of SiNR, a gap is opened in the corresponding edge states;
however, another pair of gapless edge states with opposite
spin are still protected by the time-reversal symmetry. The
computations also indicate that the conductance plateau and
spin polarization are quite stable against the NM Anderson
disorder.
The structural and electronic properties of ASiNR can be
tailored by the periodic 1V or 2V [184]. In particular, a 1V
or parallel-oriented 2V can change a direct semiconductor
ASiNR to an indirect one. But either a 1V or 2V is unable to
modify the NM nature of ASiNR. Interestingly, the electronic
properties are independent of the vacancy positions relative
to the edge of the nanoribbon. DFT based first principles
calcul­ations on ASiNR perforated with periodic nanoholes

26
Rep. Prog. Phys. 79 (2016) 126501
have indicated [189] that the band gaps exhibit an oscillatory
behavior and its magnitude is strongly dependent on the posi-
tions of nanoholes relative to the edge of the nanoribbons.
The effect of the Ruderman–Kittel–Kasuya–Yosida interac-
tion between two adatoms magnetic impurity placed on ZSiNR
in the presence of an electric field has been studied [190]
recently in the framework of a TB Hamiltonian. The study
has revealed that the zero energy states of ZSiNR are signifi-
cantly enhanced when the impurities are placed on the zigzag
edges rather than on the sheets. The ground state is predicted
to exhibit spiral FM or AFM depending on the magnitude of
the electric field. This theoretical calculation further indicates
a route to probe the interactions experimentally. Recently, the
effect of local torsional deformation of 11-ASiNR has been
studied via DFT combined with non-equilibrium Green’s
function (NEGF) method. With variations of torsional angle
from 0 to 120, 11-ASiNR however maintains a well-defined
honeycomb lattice structure. The study of the transmission
coefficient indicates that ASiNR behaves like a conductor with
current increasing linearly with applied bias voltage. The sta-
ble transport properties of 11-ASiNR are indicative of promis-
ing good elastic material for stretchable electronics [191].
3.1.4. Nanodisks.  Nanodisks are those materials in the
nano-meter scale which have closed edges. Nanodisks hav-
ing hexagonal symmetries are mainly constructed from sev-
eral benzene rings [192]. For the construction of nanoribbons,
nanodisks are an integral part. Nanodisks can be obtained by
soft-landing mass spectrometry [193]. Zero energy states in
DOS of nanodisks play an important key role in controlling
the electronic properties of the disks. Ezawa [194, 195] stud-
ied the electronic properties of graphene nanodisks by search-
ing these zero energy states. It has been found that among
typical nanodisks, only zigzag trigonal (ZT) nanodisks have
degenerate zero-energy states, and also it shows FM, where
the degeneracy can be controlled arbitrarily by changing
the size appropriately. A very interesting observation in this
regard is that the relaxation time is quite large in spite of its
small size in ZT nanodisks. In the case of graphene nanodisks,
the number of zero-energy states, ζ 0 , is given by the inequal-
ity, ζ 0 ⩾ 2| NA − NB|, where NA(NB) is the number of sites in
the A (B) sublattice. It has already been noted that [196],
if there is a particle hole symmetry in the system, the num-
ber of positive (ξp) and negative (ξn) energy states become
equal. If N is the total number of sites (N = NA + NB), then
the number of zero energy states (ξ0) can be determined as
ξ0 = N − ξp − ξn = N − 2ξp. Therefore, if N is odd, then
there exists at least one zero energy state. Now, because of
the spin degree of freedom, the states emerge in pairs com-
monly known as Krammers pairs. Thus, ξp and ξ0 are even.
As a result, the counting rule establishes simply that there is
at least one zero energy Krammers pair when N is odd. There-
fore, we can state that the system obeying particle-hole sym-
metry along with time-reversal symmetry, the number of zero
energy state is given by,
ξ0 ⩾ 2 × ( | NA − NB|  mod 2)
(18)
27
Review
This inequality is only applicable to the graphene lat-
tice, since the Hamiltonian is bipartite with NN interactions
[197]. In the case of DFT calculations, the vacancies are
repeated in each supercell, and then the number of supercell
n can be equated with the imbalance in the number of atoms
in the two sublattices (n = 2| NA − NB|). In other words, n
zero modes will appear in BZ at E  =  0 in the form of a
dispersionless band. Note that if the hopping beyond NN
is taken into account, or the onsite energies of the different
atoms are different, then this theorem will not hold good
[197]. Note that the theorem is not applicable to silicene
since it is not bipartite due to the presence of SOI. It will be
interesting to study the nature of the zero energy states in
the presence of SOI.
Kikutake et  al [196] have studied theoretically the edge
states in silicene nanodisks. As in [194, 195], Kikutake et al
have also studied in detail the zero energy states in silicene
nanodisks, and they compare the results with graphene nano-
disks. The authors then proceed to study the zero energy states
of ZT nanodisks for NA = 18, NB = 15, where N is odd. A ZT
graphene nanodisk has six zero energy modes according to
the inequality mentioned earlier. When the SOI term is taken,
there remain two zero modes (which are the π modes) with
the other four modes acquiring nonzero energies proportional
to λ SO. When the RI is taken into consideration, then these
two zero-energy modes disappear. The energy spectrum of
ZT nanodisks of both graphene and silicene is illustrated in
figure 19. In the case of even N, no zero energy state exists.
But in sufficiently large nanodisks, the π mode can be iden-
tified as gapless edge modes. The wave functions of the
π modes have also been studied to realize the bulk-edge cor-
respondence. Local probability amplitude |ψi| and local prob-
ability current Jij = 2Imψ∗i Hijψj for odd N of the π mode state
is also illustrated in figure 19.
It can be seen from figure 19 that the π modes are localized
along the edges. The edge states of the graphene nanodisk are
standing waves (Jij  =  0). But when SOI is considered, the cur­
rent begins to flow. Due to the time-reversal symmetry, the
resultant flow is helical. The local probability current of the
up-spin π mode circulates along the edge in a clockwise direc-
tion, while that of the down-spin π mode circulates in an anti-
clockwise direction.
Chowdhury et al [33] have studied the shape dependency
on magnetic and optical (discussed later) properties of silicene
nanodisks by using DFT. Different shapes of silicene nano-
disks studied are depicted in figure 20. Apart from the shape,
all these structures differ from each other by the total number
of atoms as well as the number of atoms in the edges. In order to
understand the various optical properties of a system, it is first
worth paying attention to the DOS of the system. In ­figure 21
we have plotted the DOS of ZT and bowtie shaped (BS) nan-
odisks. It was observed that ZT and AT exhibit zero energy
states consistent with the work by Ezawa [194]. Inherent trig-
onal symmetry is responsible for the formation of zero energy
states in those structures. The emergence of zero-energy states
indicates that those nanodisks are metallic in nature. Here it
is notable that for a class of smooth decaying potentials, zero
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 19.  (a1), (a2) Local probability amplitude and current of the up-spin π mode, when N is odd. We have taken λ SO = 0.1t, λR = 0 for
illustration. ((b)–(d)) Energy spectra with parameters are shown within figures. The vertical axis is E/t, and the horizontal axis is the index
of the eigenstates. The authors have taken NA = 18, NB = 15. There are six edge modes (green) in the graphene nanodisk and two π modes
(red) in the silicene nanodisk. (Reproduced with permission from figure 1 in [196]. Copyright (2013) by the American Physical Society.)

Figure 20.  Different structures of silicene nanodisks: (a) zigzag triangular/trigonal (ZT) (N  =  13, Ned = 9), (b) armchair triangular/trigonal
(AT) (N  =  18, Ned = 12), (c) diamond shaped (DS) (N  =  16, Ned = 10) and (d) bowtie shaped (BS) (N  =  20, Ned = 12), where N is the total
number of atoms in the corresponding nanodisk and Ned is the number of atoms at the edges. (Reproduced with permission from figure 1 in
[33]. Copyright (2015) Elsevier.)

energy states exist in graphene quantum dots and rings with-
out any application of a magnetic field [194]. While studying
the magnetic properties of the nanodisks, it is worth point-
ing out that only ZT possess the maximum magnetic moment
(shown in table 5). All the other structures have a vanishing
magnetic moment. The origin of this high magnetic moment
can be traced back as the occurrence of zero energy states in
the ZT nanodisk. It is now believed that Coulomb exchange
interaction plays an important role to align the spins in a ZT
nanodisk in a particular direction. An AT nanodisk also has
zero energy states but an even number of edge atoms force it
to be non-magnetic in nature. For similar reasons, diamond
shaped (DS) and BS nanodisks are non-magnetic in nature. A
ZT nanodisk has nine atoms at the edges, so it is expected to

28
Rep. Prog. Phys. 79 (2016) 126501
Figure 21.  DOS per atom for different structures of silicene nanodisks: (a) ZT, (b) BS. In the inset of (a) zero energy states between an
energy interval have been depicted. (Reproduced with permission from figure 2 in [33]. Copyright (2015) Elsevier.)
1
give 9 × 2 µ B = 4.5µ B magnetic moment for FM spin align-
ment according to the Hund’s rule. This value is very close
to the value that we have obtained through DFT calculation.
Rahaman et al [198] have also given a similar argument along
with DFT calculations due to an Sn vacancy in SnO2. Because
of the presence of a large magnetic moment in the ZT nano-
disk, one may think of it as a potential candidate for future
spintronic devices.
3.2.  Silicene under a transverse electric field
As has been mentioned, the electronic properties of silicene in
the presence of a vertical electric field can be tuned for pos-
sible application as an FET. In contrast to graphene, a bandgap
opens for silicene due to the lower symmetry of the buckled
structure. In other words, the two atoms in the unit cell feel to
be naturally different electric potentials since they are at dif-
ferent heights due to buckling.
It is possible to open a bandgap in semimetallic low-
bulked silicene and germanene monolayers via an external
vertical electric field E⊥ , while it is not possible in a semi-
metallic planar graphene monolayer. In particular, when E⊥ is
zero, then the CB and VB touch linearly at the K point giving
rise to a zero band gap and zero effective mass. However,
−1
Ni et  al [308] have demonstrated that at E⊥ = 0.51 V Å ,
a band gap of 0.08 eV is opened and doubled at the value of
−1
1.03 V Å . In figure 22, we represent the numerical results
for the opening of a band gap in silicene under the external
vertical fields. It is clear from this figure  that the buckling
parameter increases (see figure 22(c)) non-linearly with the
field. Now let us try to understand the effect of the field on
silicene and graphene from some basic point of view as given
by Drummond et al [309]. The essential effect of an electric
field is to break the symmetry between the A and B sublat-
tices of a silicene honeycomb structure, thereby resulting in
opening a gap in the staggered sublattice potential in the elec-
tric field E⊥ leading to various interesting intriguing phenom-
ena. In the language of a simple NN TB model, this is taken
as an energy correction to onsite energies in such a way that
29
Review
Table 5.  Table for magnetic moment in Bohr magneton (µ B) for
four differently shaped silicene nanodisks.
Structures Magnetic moment (µ B)
ZT 3.969
AT 0.000
DS 0.000
BS 0.006
Note: Reproduced from table 1 in [33]. Copyright (2015) with permission
Elsevier.
it is positive for the A sublattice but negative for the B sublat-
tice. This difference in onsite energies in the vicinity of the
corners of BZ amounts to the modification of the spectrum as
E± = ± (∆z /2)2 + (v Fp)2 , where ∆z = EA − EB and p is the
momentum of the electron. It should be noted that by apply-
ing this external vertical electric field, graphene still remains
in its zero-gap semimetallic character since its two sublat-
tices remain equivalent, or the A and B sublattices remain
in the same plane (planar geometry). As a consequence, the
biased monolayer graphene did not function as an effective
FET. However, because of the variation of the effective band-
gap of monolayer silicene as a function of an external electric
field, one can think of it as a more suitable candidate for FET
devices. The inequivalence of the sublattice in graphene has
also been noticed [29] in site specific B and N-doped gra-
phene for the opening of a band gap. This vertically perpend­
icular electric field also opens a gap in germanene because of
the breaking of this same symmetry between the two Ge lay-
ers formed by the atoms in the alternating corners of buckled
hexagons.
Drummond et  al [309] have chosen DFT calculations of
the band gap for Dirac-type electrons in silicene opened by
this electric field using a combination of top and bottom gates
(shown in figure  23) most suitable for direct device applica-
tions. A non-linear variation of the calculated band gap with
the inverse of the box-length is shown in figure 23 for a par­
ticular value of the external field. The modification of the band
structure at the Dirac point for two non-zero electric fields
with zero electric field is compared in figure 24. Further, at the
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 22.  (a) Top and side view of the silicene monolayer. (b) Variation of buckling distance with the vertical electric field. (c) Opening
of the bandgap under the application of the field. (Reproduced with permission from [308]. Copyright (2012) by the American Chemical
Society.)

Figure 23.  (a) Atomic structure of silicene, along with a sketch of the charge density for the highest occupied VB in the vicinity of the
Dirac (K) point. (b) Variation of DFT–PBE band gap with variation of inverse of box length in the z-direction in transverse electric field
−1
strength of 0.26 V Å . (Reproduced with permission from [309]. Copyright (2012) by the American Physical Society.)
−1
low field E⊥ ≈ 20 mV Å , silicene was shown to undergo a calculations also yield an SO gap (LDA-1.4 meV; PBE-1.5
meV) quite consistent with the existing literatures. However,
trans­ition between a topological and a simple BI. However, for
−1 the calculations carried out by this group [309] showed that the
electric fields more than about 0.5 V Å , the band gap starts
band gap depends on the vacuum spacings between the adja-
to close at the Γ point, and hence the system becomes semi-
cent layers. Later it was demonstrated that instead of the plane
metallic (shown in figure 24(c)), leading to a transition from
a BI to a semi-metallic. A linear variation of this DFT band wave basis in DFT, if one uses the local atomic orbital basis,
gap with an electric field has been indicated in figure  24(d). then the band gap under this field does not depend [199] on
Generally, the DFT calculations predicted that the gap opening the vacuum spacings between the layers (shown in figure 25).
is initially linear in the field; however, later it becomes inher- Further, the spin-polarized calculations [199] have predicted
ently non-linear. This behavior can be understood clearly from that silicene uniformly covered with Ti atoms at 1/8 cover-
invariant and symmetry considerations of the band structure age is spin-polarized, having a magnetic moment of 3µ B, and
[104]. It is also evident from figure 24(d) that although there is is a half-metal. This indicates that it is a metal for one spin
the possibility of a minigap, its value is strongly reduced by the direction and a semiconductor for the opposite spin direction.
polarization of the atomic layer. These Hamiltonian based DFT Therefore, one can visualize this material as a spin valve.
30
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 24. (a)–(c) Electric field induced minigap in silicene and (d) variation of band gap with electric field with various parametrical
values of Lz. (Reproduced with permission from [309]. Copyright (2012) by the American Physical Society.)

Figure 25.  Linear variation of the band gap with field but independent of the vacuum spacing between the layers. (Reproduced with
permission from [199]. Copyright (2013) by IOP Publishing Ltd.)

The electric field can tailor the band gap in such a way that
silicene can transform from a TI to a BI leading to topologi-
cal quantum phase transition [102, 110]. Including the SOC
in the Hamiltonian, it has been demonstrated [102] that the
gap decreases linearly to zero at a certain critical field Ec and
then increases linearly with the perpendicular field. It has been
further argued that it is a TI for E⊥ < Ec and a BI for E⊥ > Ec.
The calculations of the band structure of silicene at the critical
electric field Ec have revealed that the band for up-spin (down-
→
spin) electrons are gapless (gaped) at the K point but gaped
→
(gapless) at the K ′ point. In the case of an inhomogeneous
electric field, however, novel helical zero modes appear and

31
Rep. Prog. Phys. 79 (2016) 126501
Figure 26.  Initial unrelaxed configurations of the single (1V), double (2V), and triple (3V) vacancies. (Reproduced with permission from
figure 5(a) of [218]. Copyright (2013) by the American Physical Society.)
Figure 27.  Relaxed configurations and the isosurface of (left) single (1V), (middle) double (2V), and (right) triple (3V) vacancies. The
−3
value of the isosurface was taken as 0.01 e  Å . (Reproduced with permission from figure 5(c) of [218]. Copyright (2013) by the American
Physical Society.)
these modes can be suitably controlled by the electric field
locally to the critical field Ec. The finite frequency conductiv-
ity study of silicene by the usual Kubo formalism can be used
to differentiate between the TI and BI phase [200]. Moreover,
this formalism can, in principle, be utilized to identify the
critical point of transition and allow for an experimental deter-
mination of the strength of SOC in these 2D exotic systems.
A TB calculation has been attempted recently for doped and
biased silicene to predict a tunable electrical resistance mat­
erial transforming from a normal metallic phase to a fully
insulating one [201].
The applied vertical field can also significantly change [128]
the Si–H bond length in silicane. In particular, the H-atom at
the high potential side is desorbed while the H-atom at the
low potential keeps bonded. In this sense, an external elec-
tric field can be a tool to produce single-side H-silicene from
silicane. It is believed that the band gap of silicane under this
vertical field will also change considerably and may undergo
some interesting phase transitions with a variation of the
field. The chemical activity of H-silicene can be significantly
modified by such a perpendicular electric field. In particular,
a recent study has indicated [202] that the energy barrier of
32
Review
dissociative adsorption of a H2 molecule on silicene can be
reduced by applying a positive electric field. This field in such
a case acts as a catalyst to facilitate the silicene hydrogenation
reaction. It is to be noted here that the negative electric fields
have a converse effect on this reaction to increase the reaction
energy barrier. This can be regarded as an alternative method
to hydrogenate silicene for opening its band gap.
3.3.  Silicene with vacancy
A minute amount of defects can drastically change its electri-
cal, optical and magnetic properties. In the recent past, defect
driven ferromagnetism was one of the most discussed issues.
In oxide semiconductors and other related issues, phenom-
ena which originate from defects offer huge possibilities for
study both theoretically and experimentally [203]. In this sec-
tion, we would like to present some important theoretical and
experimental surveys on structural defects in planar or buck-
led silicene NSs/ribbons and discuss the influence of these
defects on the physical properties of silicene.
Among different types of defects, vacancies are local
defects in nature and they are most frequently observed in
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 28. (a)–(c) Supercell of divacancy induced silicene NS with three different configurations. (Reproduced from figure 1 in [31], with
permission of The Royal Society of Chemistry.)

Figure 29.  (a) Spin polarized electronic DOS of divacancy induced silicene NS. (b) Comparison of values of the magnetic moment using
LDA and GGA schemes. (Reproduced from figures 3 and 5 of [31] respectively, with permission of The Royal Society of Chemistry.)

crystal, which profoundly alter the mechanical and electrical
properties of materials [204–210]. Vacancy defects are formed
during the synthesis of the material [211–214] or sometimes it
is purposefully created within the sample to enhance some of
its properties [215–217]. Ozcelik et al [218] have studied the
reconstruction process of asilicene NS after the introduction
of 1V, 2V and triple vacancy (3V) by using finite temperature
MD simulation. Figure 26 depicts the unrelaxed structures of
1V, 2V and 3V in silicene.
The defected SLs are then relaxed by both the self-con-
sistent-field conjugate gradient method and MD simulation
at 300 K. Both spin-polarized and unpolarized calculations
have been performed. In the framework of spin-unpolarized
calculations on a silicene sheet with 1V, it was found that the

33
Rep. Prog. Phys. 79 (2016) 126501 Review

NM ground state is more favorable. In the unrelaxed struc-

ture with 1V, the atoms surrounding the vacancy have three
DBs. After relaxation, these atoms move towards the center of
the vacancy and form bonds with each other, as shown by the
dashed lines in figure 27.
Also due to reconstruction, three pentagons and three hexa-
gons appear around the vacancy. At the end, the DBs get satur­
ated and two-fold coordinated silicon atoms surrounding the
vacancy become fourfold. This gives a symmetric structure
around the vacancy. This symmetric structure also gives rise
to a symmetric distribution of the magnetic moment. Thus,
the ground state becomes a singlet state with a net zero mag-
netization. In the case of 2V, there are four two-fold coor-
dinated atoms surrounding the hole, each with a DB. After
reconstruction, four DBs are saturated in pairs to form two
Si–Si bonds which lower the formation energy. As there are
no DBs left after relaxation, so silicene with 2V is chemi-
cally inactive. For the 3V case, among five DBs, four of them
are combined in pairs to form two Si–Si bonds. The fifth DB
remains unpaired which makes it chemically active. All these
structures are found to have a non-magnetic ground state.
Gao et  al [219] have also studied the mobilities, electronic
and magnetic properties of vacancy induced silicene. They
have established that 1V has much higher mobility than 2Vs
and two single vacancies are very likely to coalesce into one
double vacancy to lower the energy. Also 2V may induce a
small gap in silicene, while a 1V defect may bring a trans­
ition from semi-metallic silicene into metallic silicene. Li
et  al [182] have reported the coalescence tendency of small
vacancy defects and the formation of highly stable vacancy
clusters in FS silicene. The formation energy of vacancy clus-
ters is decreased dramatically when the defects are arranged in
a line and form extended line defects. It is demonstrated that
the formation of the double–pentagon double–heptagon and
Figure 30.  Variation of the total energy at various steps during the
triple–pentagon triple–heptagon in extended line defects in a dissociation process of (top) H2 on silicene, (middle) O2 on silicene,
silicene sheet is significantly easier than in graphene. Due to and (bottom) CO on silicene. (Reproduced with permission from
buckling, silicene requires a lower SW transformation barrier figure 4 of [221]. Copyright (2014) by the American Chemical
than graphene. It is also found that the disordered structures Society.)
with under-coordinated Si atoms (which give rise to DB) have
higher formation energy and thus have less stability. Further 2V case when using the GGA functional. But the magnetic
studies with various configurations of silicene NSs having 1–6 moment is not quite significant while using LDA. The magn­
atom vacancies have revealed that instantly removing a num- etic moment of various structures are shown in figure  29(b)
ber of atoms from silicene causes bending or rippling of the for both LDA and GGA functionals.
monolayer NS, which considerably reduces its surface area. A systematic study employing the DFT and NEGF method
The rippled structure decreases the energy of the systems and has been employed [220] to compute the structural, elec-
might stabilize the vacancies in the silicene layer. Majumdar tronic and transport properties of graphene and silicene in
et  al have studied the magnetic properties of 1V and 2V the presence of SW, 1V, 2V-585, 2V-555777 defects. Here
induced planar silicene NSs, along with Al and P doping from 2V-585 represents two pentagons and one octagon while
first principles calculation [31]. Here three configurations of 2V-555777 represents three pentagons and three heptagons.
the 2V case have been considered, illustrated in figure 28. Although the defects give qualitatively similar fingerprints in
As mentioned earlier, Ozcelik et al [218] have found the transport properties in both the systems, defects in silicene
non-magnetic ground state of buckled silicene. But here, have smaller formation energy in silicene due to its buckling
planar silicene structures have been considered without any characteristics. Identification of various defects is possible
buckling which exhibit a magnetic ground state when induced via STM and in the case of silicene, I– V characteristics seem
by 2V, but a non-magnetic ground state when 1V is intro- to be a better benchmark for the identification of defects.
duced in the pristine system. The spin-polarized DOS plotted Local current densities are also enhanced by the resonances
in ­figure 29(a) shows the magnetic ground state clearly. The created by defects leading to local heating and degradation of
magnitude of the magnetic moment is also significant in the the material.

34
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 31.  In-plane PDOS analysis of the effect of (a) the monoatomic vacancy concentration, and (b) the size of a vacancy cluster for a
silicene sheet. Overall PDOS for bulk silicon is plotted by the dashed line for comparison. ρ is the concentration of monoatomic vacancies.
(6,448) denotes that a 6-atom cluster was removed from a 448-atom cell. (Reproduced with permission from figure 5 of [226]. Copyright
(2012) Copyright EPLA.)

Gurel et  al [221] have studied the interaction of H2, O2,

CO, H2O and OH with 1V defects of silicene. They have
demonstrated that the atoms around the vacancy reconstruct
themselves in such a way that chemically active sites are cre-
ated. Besides, H2, O2 and CO molecules can dissociate around
defects, whereas H2O and OH remain intact and stay attached
to the vacancy site as a molecule. The dissociation process of
H2 starts once it overcomes a barrier of energy 1.3 eV at the
critical height of 1.1 Å above the plane of silicene. However,
for the O2 molecule, the energy barrier is low (0.05 eV) while
the range of attraction is rather long. For the CO molecule,
once it overcomes the energy barrier, the CO molecule is also
attracted towards the vacancy site of silicene. The carbon atom
of the molecule tends to complete the hexagon having five
Si atoms by substituting the missing Si atom. The variation
of total energy during various dissociation processes of H2,
O2 and CO are illustrated in figure 30. Through DFT calcul­
ations, Li et al [222] have studied the geometrical and elec-
tronic structure of silicene with 1V, placed on a h-BN sheet
and Ag(1 1 1) surface. It has been noticed that due to weak Figure 32.  The calculated real (ε1) and imaginary (ε 2) part of the
vdW interaction with the h-BN sheet, there exist two kinds of dielectric function of silicene: parallel (top), perpendicular (middle)
1Vs with a closed five and nine membered pair of rings. components and total (bottom). (Reproduced with permission from
Martins and Alves [223] have developed an extended figure 5 of [235]).
Huckel theory to study the electronic properties of pristine
group IV materials and compare the results with DFT. They 2V in the sheet’s center reduces 18–20% in fracture stress
have also studied the electronic properties of silicene with and 33–35% in fracture strain. It has also been shown that the
1V. It has been found through their calculation that extended Poisson’s ratio in the zigzag direction is always higher than
Huckel theory offers a remarkably reliable description of the that in the armchair one. Li and Zhang [226] have studied the
electronic structure of these materials. Thus it offers an afford- κ of the vacancy induced silicene NS. They have found that
able way for studying large systems for which DFT calcul­ for the lowest 1V concentration ρ of 0.22% (i.e. one of the
ations would be computationally expensive. Le and Nguyen 448 atoms is removed), the reduction in κ can be remarkable
[224] have studied the mechanical properties of silicene with (by 78%) compared with a pristine one. As the vacancy sites
a vacancy. The Tersoff potential [225] has been applied to increase to 0.45% and 1.56%, normalized in-plane κ (i.e. the
model the interatomic interaction. The strain has been applied the ratio between the in-plane κ of the defective sheet and
to both in the zigzag as well as in the armchair direction. It that of the pristine silicene sheet) can be reduced to  ∼0.50
has been noticed that the fracture strength is significantly and  ∼0.28, respectively. Furthermore, when the vacancy con-
reduced by a single 2V. The vacancy has been created at the centration increases from 1.56%–4.5%, the reduction in nor­
center of the sheet by removing two adjacent Si atoms. One malized in-plane κ is only  ∼0.10. While analyzing the effect

35
Rep. Prog. Phys. 79 (2016) 126501
of the vacancy on the PDOS, it has been observed that the
high frequency parts of the PDOS near 18 THz are remark-
ably reduced, leading to lower κ, because the optical modes
can also carry some heat. Also a remarkable broadening of the
acoustic phonon modes has been found near 6 THz and 12.5
THz with the increase of the vacancy concentration and hole.
In the case of larger contractions or the larger sized vacancy
defects, the valleys and peaks in the PDOS curve between 10
and 16 THz almost disappear (see figure 31).
Due to the flattening of the PDOS curve (between 10–16 THz)
mentioned above, a reduction in the lifetime or the mean
free path of the related phonon mode is observed. The scat-
tering of the phonon due to the vacancy defect is respon-
sible for such reduction in lifetime. Due to the presence of
the vacancy, some acoustic vibration modes become localized
and so adversely contribute to κ. Berdiyorov and Peeters [227]
have studied the thermal stability of vacancy induced silicene.
It has been established that even 1V can reduce the thermal sta-
bility of silicene by more than 30%. In this case, the system
is found to be stable up to 1000 K. After reaching the critical
temperature, it transits to a 3D-amorphous configuration with
dominating sp3 hybridization. The range of stability of the sys-
tem can be increased by passivating the DB of the silicon atoms
near the defects, as shown in [227]. Setiadi et  al [228] have
studied the adsorption and diffusion of Li ions through dis­
ordered silicene including 1V and 2V. It has been noticed that
the diffusion barrier through silicene is significantly lower than
that of graphene, with a value of 0.05 eV for 2V and 0.88 eV
for 1V. As a consequence, it might be used in Li ion batteries
because of its low diffusion barrier energy both in the surface
and in the vacant site. The silicene sheet with 2V [229] is shown
to be inert to several gas molecules. These gas molecules inter-
act very weakly via vdW interaction. The diffusion barrier of
the H2 molecule through 2V was found to be 0.34 eV [229].
This actually suggests that a hydrogen molecule can perme-
ate the porous silicene at a moderate temperature and pressure.
The authors [230] have also studied the diffusion mechanism of
noble gases through porous silicene via DFT. It has been indi-
cated that silicene with 2V can be used for noble gas separa-
tion with high permeability and selectivity. Syaputra et al [231]
have investigated the electronic band structure of SW defected
silicene under an external electric field. The variation of the band
gap with an external electric field indicates that the band gap is
largest (228 meV) at 2 V nm−1. Beyond this magnitude of the
electric field, however, the band gap decreases and goes to zero
at 5 V nm−1.
4.  Anisotropic optical properties
Any elegant many body theory of calculating dielectric func-
tions involves many body wavefunctions or Green’s func-
tion and excited electronic states. However, it is well known
that formal DFT theory relies only on the ground state of a
many particle system. Thus, the study of electronic excita-
tions strictly speaking is outside the realm of DFT. However,
DFT theory used for optical properties can be regarded as a
first step for sophisticated theories related to excited states
36
Review
of electrons. Besides, sophisticated theories compared to
DFT are time-consuming. In this sense, to get a first hand
idea about optical properties of a system, DFT with its legiti-
mate approximations, can serve as a simple tool compared to
other techniques. In fact, DFT results seem to be qualitatively
reasonable [232] so long as we are not concerned about the
detailed fine structure of optical spectra. The EELS of pristine
graphene computed under GGA [30] match reasonably well
with experimental observation [233].
Optical properties of any system are in general calculated
with the help of frequency dependent complex dielectric func-
tion: ε (ω ) = ε1(ω ) + iε 2(ω ). ε1(ω ) and ε 2(ω ) are not independ-
ent on each other. They are connected to each other by the
Kramers–Kronig relation. In numerical simulation, the imagi-
nary part of the dielectric function is calculated with the help
of a time dependent perturbation theory in the simple dipole
approximation. In the long wavelength limit (q → 0), the
imaginary part of the dielectric function is given by,
2
2e 2π
ε 2 (ω ) = ∑ ⟨ψVB
Ω ε 0 k,CB,VB
CB CB VB
k | u .r | ψk ⟩ δ (E k − E k − ω ).
→ →
(19)
k
In the above expression (1), E CB and E kVB are the energy of the
electrons at CB and VB respectively at a particular k point.
ω is the frequency of the electromagnetic (EM) radiation in
the energy unit. Ω represents the volume of the supercell and
ε 0 is the free space permittivity. u→ and → r denote the polariza-
tion vector and position vector of the EM field respectively.
The matrix element of this dot product of these two vectors
is computed between the single electron energy eigen states.
Since the magnetic field effect is weaker by a factor of v/c,
the transition matrix elements between the eigen states of CB
and VB have been calculated only due to the electric field.
Phonon contribution, local field and excitonic effects are not
taken into consideration. By definition, the imaginary part of
the dielectric function (ε 2(ω )) is positive for any polarizations
and frequency [175, 234].
4.1.  Doped and nanodisk silicene systems
Chinnathambi et al [235] have studied the optical properties
of pristine silicene, H-silicene and silicene under the applica-
tion of a transverse electric field. It was found that the opti-
cal properties strongly depend on the polarization of light,
whether the direction of the propagation of the EM field is
in the plane of the silicene sheet (parallel polarization) or
perpend­icular to the silicene sheet (perpendicular polariza-
tion). Here it should be mentioned that the static values of the
real part of the dielectric function (ε1(0)) for a pristine silicene
NS (32 atoms) are 5.4 and 1.6 for parallel and perpendicular
polarization respectively, as seen from figure 32.
It is also evident from figure 32 that parallel and perpend­
icular components respectively dominate the lower (below
approximately 5 eV) and higher (above 5 eV) energy regime.
The inherent optical anisotropy is a consequence of the 2D
nature of the buckled silicene sheet. A comparison of the opti-
cal absorption spectra of silicene with the application of an
Rep. Prog. Phys. 79 (2016) 126501
Figure 33.  The optical absorption spectra of silicene: (a) without
−1 −1
electric field, (b) with 0.25 V Å (c) with 0.5 Å ,(d) with 1.0 V Å
and (e) hydrogenated. (Reproduced with permission from figure 6
of [235]).
electric field has been performed recently [235], as shown in
figure 33. The optical absorption spectra of silicene show two
major peaks : (i) a sharp peak at 1.74 eV due to the trans­
ition from π to π∗ states, and (ii) a broad peak in the range of
4–10 eV due to the excitation of σ states to conduction bands
(shown in figure 33).
The broad energy range of this transition is due to the large
band width of both σ and σ∗ states. The absorption spectra
clearly show that there is no absorption of light below a cut-
off frequency. This is because of the breaking of the symmetry
between two sublattices due to the application of an external
electric field. This cut-off value, however, increases with the
increasing electric field strength. But the peak positions corre­
sponding to different electronic transitions remain almost
similar to those of silicene without an external electric field.
So here it can be inferred that the main effect of an external
electric field is to influence the electronic states close to the
Fermi level. By observing the optical-spectra of H-silicene, it
can be seen that there is no absorption up to a threshold value
which is equal to the band gap. The main effect of hydrogena-
tion on the absorption spectra is the disappearance of the first
peak around 1.74 eV because there are no π bands present in
the system due to hydrogenation.
Bao et  al [236] have studied the optical properties of a
three-terminal silicene-based device under the irradiation of
a circularly polarized THz EM field. It has been clearly dem-
onstrated that the dielectric function and the optical absorp-
tion spectra from the TI spin-up and spin-down subbands
are red-shifted and blue-shifted respectively with increas-
ing sublattice potential, while for BI, the spin-up and spin-
down subbands are shown to be continually blue-shifted with
increasing staggered potential. Mohan et al [92] have studied
the electronic and optical properties of strained silicene. They
Review
have considered five different ways to apply homogeneous
strains, namely, uni-axial expansion (+a), bi-axial expansion
(+a  +  b), uni-axial compression (−b), bi-axial compression
(−a  −  b) and asymmetric bi-axial (+a  −  b) strain, where ‘a’
is the magnitude of strain (e) along the direction of lattice vec-
tor a while ‘b’ is the magnitude of the strain (e) along the
direction of lattice vector b. In this study, the magnitudes of
‘a’ and ‘b’ are taken to be equal. In figure 34, the real, imagi-
nary and EELS are shown up to 12% strain.
From the imaginary part, the characteristic peaks are found
to be at 0.12 eV, 1.60 eV and 3.91 eV. These peaks correspond to
the inter-band transitions in an electronic band structure. With
an increasing magnitude of strains, the characteristic peaks at
lower energies (0–1 eV) vanish. The transitions at higher ener-
gies (above 2 eV) shifted to a lower frequency with increas-
ing magnitude of tensile and asymmetric strain. However, for
uni and bi-axial compressive strain, the trans­itions are blue-
shifted. In the case of the real part of the di­electric function, the
points where it cuts the x axis (energy) from both positive and
negative sides correspond to the collective excitations of elec-
trons. These collective oscillations, known as plasma oscilla-
−1
tions, are responsible for the occurrence of sharp peaks in the
EELS. It was found that the EELS show two major peaks. One
lies between 7 and 8 eV which is due to π + σ plasmon, and
another one is near 2 eV due to π plasmons. With the increas-
ing magnitude of applied compressive strain, the positions of
π plasmon peaks are not affected. But for tensile and symmet-
ric strain, the peaks disappeared with increasing magnitude.
With the increase of bi and uni-axial tensile strains, a red-shift
in π + σ plasmons occurred while a blue-shift is observed for
compressive strain, whereas asymmetric bi-axial strain does
not show any significant changes in the π + σ plasmons peak.
Matthes et al [51, 237] have studied the optical conductivity
of silicene along with other group IV materials. The calcul­
ations based on the independent-quasiparticle approximation
have revealed that the first peak in the optical conductivity
around 2 eV is associated with π − π∗ transition. The higher
peak near 5 eV is due to σ − σ∗ transition. Mohan et al [23]
have studied the optical properties of a monolayer and dif-
ferently stacked BLS. The electric field affects only the IR
region of the dielectric behavior. In the low frequency regime
(0–5 eV), there are no excitations of electrons for out-of-plane
polarization, while for in-plane polarization, the plasmons are
observed at very low energies (as compared to graphene) at
2.16 eV for mono­layer and at 1.48 eV for AB-stacked BLS.
Interestingly, however, there are no plasmons for AA-stacked
bilayer buckled silicene. In the case of out-of-plane polariza-
tion, the existence of multiple surface plasmon (π + σ ) peaks
around 10 eV has been noticed for both mono and buckled
BLS. The real, imaginary part of the dielectric function and
the EELS for the monolayer and differently stacked BLS for
different polarization have been illustrated in figure 35.
From the EELS depicted in figure 35, two prominent fea-
tures for in-plane polarization emerge. Firstly, the peak below
5 eV is due to π plasmons. Secondly, the peak above 5 eV
are the characteristic features of π + σ plasmons. For out of
plane polarization, the prominent resonance feature occurs
above 10 eV due to π + σ plasmons. The occurrence of the
37
Rep. Prog. Phys. 79 (2016) 126501
Figure 34.  Imaginary and real parts of the dielectric function and electron energy loss function of silicene with different types of strains at
different magnitudes (e  =  0, 0.04, 0.08 and 0.12). (Reproduced figure 8 in [92]. Copyright (2014) permission from Elsevier.)
π plasmons feature is due to the collective π − π∗ transitions,
while π + σ plasmons result from the π + σ∗ and σ − σ∗ exci-
tations. Here, it is interesting to note that the resonance peaks
occur in the lower energy in silicene than that of graphene.
Motivated by the reasonable sizes of Al and P in silicene,
recently Das et al have studied [32] the optical properties P,
Al and Al–P co-doped silicene by using DFT. For Al and P
doping, concentrations have been varied from 3.12%–15.62%
while for Al–P co-doped from 6.25%–31.25%. The imaginary
part of the dielectric function (ε 2) for 6.25% Al, P and Al–P
doped systems are depicted in figure 36.
The peaks below 3 eV energy regime originated from
π − π∗ transitions while those above 3 eV are due to σ − σ∗
transitions. The variation of the real part of the static di­electric
function (ε1(0)) with doping concentrations are shown in
figure 37(a).
A careful look at the figure for perpendicular polarization
shows an overall increasing tendency for both Al and P doped
systems. But for co-doped systems, an overall constant behav-
ior is notable. For parallel polarization, in the case of Al and
P doped systems, the inverted parabolic shape of the graph is
observed. For the P doped system, after an initial slight incre-
ment, it starts increasing and reaches a minimum at 12.50%.
For co-doped systems, a zigzag behavior is noticed. While
38
Review
studying EELS, it was found that for perpend­icular polariza-
tion, two new small yet significant EELS peaks emerge for P
doping. The emergence of these new peaks may be explained
through the buckling effect in the silicene NS. The maximum
value of the absorption coefficient for pristine silicene is
13.55 (in cm−1) at the frequency 4.07 eV for parallel polariza-
tion, whereas it is 16.35 (in cm−1) at the frequency 9.11 eV
for perpend­icular polarization. But in the doped systems, as
depicted in figure 37(b), the value of the maximum absorption
coefficient is higher than the pristine one. For parallel polariza-
tion, the absorption coefficient is blue-shifted, independent of
the doping concentrations. But for perpend­icular polarization,
for P and Al–P doped systems, a red-shift is observed in the
maximum value of the absorption coefficient.
To analyze the reflectivity spectra, we have also studied the
reflectivity modulation (RM) which is given by,
1 dR(ω )
RM =
(20)
R(ω ) dω
where R(ω ) is the reflectivity at normal incidence as a func-
tion of frequency. It is a mathematical tool used conveniently
to study the fine structures associated with the reflectivity
spectra [234] of any material. By its very definition, R(ω ) is
positive for all frequency regimes. But RM can have any sign.
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 35.  Real, imaginary part of dielectric function and electron energy loss function of monolayer, AB-stacked and AA-stacked BLS
for (a), (c), (e) in-plane polarization and (b), (d), (f) out-of-plane polarization. (Reproduced from figure 4 in [23]. Copyright (2013) with
permission from Elsevier.)

Figure 36.  Imaginary part of the dielectric function and the corresponding structure for 6.25% (a) Al doping, (b) P doping, (c) Al–P co-
doping for both parallel and perpendicular polarization. Here, the black, blue and yellow balls respectively depict the Si, Al and P atoms.

The modulation data for Al–P co-doped systems with varying
concentrations are depicted in figure 38.
The reflectivity modulation is restricted within low energy
(<4 eV) and high energy (>8 eV) for parallel and perpend­
icular polarization respectively. For P doped systems, the peak
near 10 eV changes its amplitude but its position remains fixed
with increasing doping concentrations. This is indeed a char-
acteristic feature of P doped systems. For Al–P co-doped sys-
tems, the existence of two significant peaks at 8 and 10 eV for
perpendicular polarization is important for all concentrations.

39
Rep. Prog. Phys. 79 (2016) 126501 Review

Figure 37.  (a) Variation of the static value of the real part of the dielectric function (ε1(0)) with various doping concentrations for parallel
and perpendicular polarization. (b) Variation of maximum value of absorption coefficient (A(ω )) with various doping concentrations
for parallel and perpendicular polarization with frequency measured in eV. (Reproduced with permission from figures 6 and 8 in [32]
respectively. Copyright (2014) by the Royal Society of Chemistry.)

Figure 38.  The reflectivity modulation with energy for various doping concentrations of Al–P co-doped systems for both types of
polarization. (Reproduced with permission from figure 10 in [32]. Copyright (2014) by the Royal Society of Chemistry.)

In table 6 we have verified the optical sum rule for both kinds
of polarizations. We have separately calculated the int­egral
∞ π 2
∫0 ωε 2(ω )dω and the quantity 2 ω p (ωp being the plasma fre-
quency) and later compared the two results. From the results
it can be seen that there are discrepancies between the two sets
of results. It is because of the fact that the optical sum rule is
valid for ω ′  ω which we have not considered in the calcul­
ation. The plasma frequencies ωp of the systems under study
are within the range of 4–8 eV for parallel polarization. But
they are in the range of 8–10 eV for perpendicular polariza-
π
tion. Because of this reason, the values of the quanti­ty 2 ω2p are
more for perpendicular polarization than parallel polarization.
In section  3.1.4 we have mainly discussed the electronic
and magnetic properties of differently shaped silicene nano-
disks. Here we are going to discuss its anisotropic optical
properties via DFT.

40
Rep. Prog. Phys. 79 (2016) 126501 Review

Table 6.  Table for verifying the sum rule as mentioned earlier for different concentrations of Al doping for different polarization.

Parallel Perpendicular
∞ π 2 ∞ π 2
% of defects ∫0 ωε 2(ω )dω ω
2 p ∫0 ωε 2(ω )dω ω
2 p

3.12 78.709 124.21 76.434 314.90

6.25 79.295 124.95 75.903 315.67
9.37 78.397 122.83 75.625 313.10
12.50 78.047 123.52 75.133 312.27
15.62 77.159 124.28 74.705 310.86

Figure 39.  (a) Real and (b) imaginary part of the dielectric function for AT nanodisk. (Reproduced from figures 3 and 4 in [33]. Copyright
(2015) permission from Elsevier.)

The real and imaginary parts of the dielectric function
for an AT nanodisk are depicted in figure  39. The oscilla-
tory behavior is found up to 9 eV. Beyond 9 eV, the opti-
cal response becomes very poor and all of them merge. But
for perpend­icular polarization, a sharp change is observed
around the energy range 8–11 eV. The static values of bulk
Si and silicene are respectively 11.68 and 3.9. Here in all
nanodisks the static values are less than that of bulk Si and
silicene. The different values of the dielectric functions
originate from shape aniso­tropy and edge geometry. At this
stage, it is curious to note that the significant values of the
static dielectric function come from those structures which
value of the static real dielectric function for both kind of
polarizations.
Since conventional DFT is based on frozen atom approx­
imation, it can only predict the ground state properties of a
many body system. However, by introducing appropriate lat-
tice dynamics and choosing thermally equilibrated configu-
rations, one can compute the various optical properties of
nanostructures at finite temperature [238]. MD simulations
can generate various thermally equilibrated configurations.
Using those configurations, one can compute the ensemble
average of dielectric functions in the following way [239]
1 → →

do not have zero energy states. The presence of zero energy
states make the nanodisks magn­etic but they fail to contrib-
ute to the optical anisotropy. Some essential data regard-
ing the various optical parameters of differently shaped
nanodisks are illustrated in table 7. It is found that the DS
nanodisk shows the highest value of maximum reflectivity
Rmax(ω ), static real part of the refractive index n(0) and static
real part of the dielectric function ε1(0) among all other nan-
odisks for both kinds of polarizations, whereas the AT nano-
disk shows the most poor optical response among them. It
has been noticed that the DS nanodisk has the maximum
ε 2(ω, T ) = ∑ ε 2(ω, Ri )e−E (Ri )/ kBT .
(21)
Z i
→ →
Here, Z is the partition function (e−E (Ri )/ kBT ) and E (Ri ) is
the total energy of the thermally equilibrated configurations.
Figure  40(a) depicts the typical band structure and DOS
of silicene used to compute the dielectric function. In fig-
ure  40(b), the computed dielectric function of silicene for
two different temperatures, apart from zero one, is shown for
parallel as well as perpendicular polarizations. It is clearly
marked that the absorption peak around 1 eV for paral-
lel polarization is significantly enhanced with an increase

41
Rep. Prog. Phys. 79 (2016) 126501 Review

Table 7.  Table for maximum reflectivity Rmax(ω ), static real part of the refractive index n(0) and static real part of the dielectric function
ε1(0) for different systems and for different polarizations.
ZT AT DS BS
Parallel Perpendicular Parallel Perpendicular Parallel Perpendicular Parallel Perpendicular
Rmax(ω ) 0.098 93 0.025 22 0.064 00 0.024 97 0.158 14 0.074 19 0.114 56 0.030 57
n(0) 1.728 98 1.045 61 1.541 49 1.043 23 2.033 24 1.074 94 1.981 90 1.049 03
ε1(0) 2.985 22 1.093 30 2.376 18 1.088 33 4.133 97 1.155 50 3.926 03 1.100 48

Note: Reproduced from table 2 in [33]. Copyright (2015) with permission from Elsevier.

Figure 40.  (a) Electronic band structure and DOS of silicene at 0 K. (b) Temperature dependent anisotropic dielectric functions of silicene
for parallel as well as perpendicular polarization. (c) Comparison of temperature dependent DOS of silicene. (Reproduced with permission
from figure 2(b), 3(b) and 4(b) in [238]. Copyright (2015), AIP Publishing LLC.)

of temperature. It is due to the zero energy gap and intra-
band transitions in silicene. But, for perpendicular polari-
zations, several absorption peaks at 0K are smoothened out
at higher temperatures. With an increase of the strength of
lattice vibration, more free carriers are thermally excited
to take part in the intraband transitions. It is observed from
figure  40(c) that such electronic states aggregate near the
energy gap with an increase of temperature. This establishes
the fact that at lower photon energy, the intraband transitions
dominate the optical absorptions spectra. This approach will
help one to compare the experimental results of the di­electric
function with numer­ically computed ones, and can also serve
as a benchmark for the various approximation schemes used
in DFT.

42
Rep. Prog. Phys. 79 (2016) 126501 Review

8π 2ω
∑ ∑ |MCV(k )|2 δ (ECB(k ) − EVB(k )
→ → →
A(ω ) =
(22) cS CB,VB k
→
− ω(k ))
Here, S is the area of the system and the matrix element
→
MCV(k ) is given by
→ →
CB, k | eˆ ⋅ p→ | VB, k
→
MCV(k ) =
(23) → → .
ECB(k ) − EVB(k )
Note that instead of band dispersion, one only requires ab ini-
tio Kohn–Sham single particle eigenvalues and eigenfunctions
to compute this matrix element. In longitudinal gauge (LG)
and transverse gauge (TG), the matrix element takes the fol-
lowing forms as given by
Le → → → → →
M CV CB, k | e q ⋅ r | VB, k
(k ) = →lim
|q→| q →0
→ →
(24) → q ⋅p
CB, k | q | VB, k
→

→ e
M TCV(k ) = → → .
m ECB(k ) − EVB(k )
Figure 41.  Universal transmittance (T  =  1  −  A) of SL and bilayer
graphene as a function of wavelength. Here, α is the fine structure In all these numerical computations, however, many body effects
constant. (From [240]. Reproduced with permission from AAAS.) and excitonic effects are neglected. Besides, the only vertical
transitions in the band diagram are taken into account. Now, near
→ →
Dirac points (K , K ′), the matrix elements can be simplified as
4.2.  Universal feature of optical absorbance
→ → m →
(25) CB, k | p→ | VB, k ≈ ∇K EVB(k ) = mv F
Soon after the discovery of graphene, it was realized that a fine 
e2 →
structure constant (α = c ) defines the visual transparency independent of k . In such a situation, the absorbance can be
[240] of graphene, not only for single but also for bilayer. In written as
figure 41, we depict schematically the transmittance of SL and α → → → →
BL graphene as a function of wavelength and the universal A(ω ) =
m2ω ∫BZ  d2k   j∑
= x, y
| < +, k | pj |−, k > |2 δ (E+(k )− E−(k ))
feature is correctly demonstrated in terms of πα. (26)
Based on this prominent feature of graphene, it was quite
where we have used  +  and  −  for CB and VB respectively.
natural to explore such universal features of the absorbance → →

in other group IV elements, such as silicon or germanium, in
their 2D structure. The absorbance of graphene, silicene and
germanene confirms the universal character which is inde-
pendent of the corresponding Fermi velocity and buckling
[241].
All these clearly state that as ω → 0 the absorbance
A(0) = πα. It is known [241] that there exists considerable
deviation of absorption spectra for higher frequencies in the
case of silicene and germanene in comparison to graphene
[241]. This universal feature can be simply understood [51,
241–243] from the imaginary part of the dielectric function
as follows.
The absorption coefficient A(ω ) has the dimension of
inverse of length. An alternative definition of the absorb-
ance used for the ab initio calculation of 2D materials in a
ωLε
dimensionless form is given as A(ω ) = c 2 , with L being
the appropriate size under consideration. With the help of
first order time-dependent perturbation theory, the Fermi–
Golden theory yields [244] in the long wavelength limit
(q → 0)
Now, using ∑j = x, y| < +, k | pj |−, k > |2 = (mv F )2 around the
Dirac points, the absorbance can be further reduced to a sim-
ple integral form as
2v2Fα
ω
A(ω ) = ∫
 d2(∆k ) δ (2v F |∆k |−ω )
(27)
2v2Fα πω
    = × = πα.
ω 2v2F
Thus, we notice that the universal feature of the absorbance
originates from the fact that at the Dirac points, two bands
isotropically cross each other linearly. It might appear that the
absorbance (see equation (24)) may depend on the choice of
LG or TG. However, the numerical results shown in figure 42
indicate clearly that the absorbance is indeed a gauge invariant
quantity. Thus, the zero frequency limit of the absorbance of
all these group IV elements turns out to be independent of the
choice of the gauge, Fermi velocity, the degree of sp2 and sp3
hybridizations and finally, the amount of buckling. This uni-
versality also points out that graphene-like symmetry (D3D) is
preserved in these materials.

43
Rep. Prog. Phys. 79 (2016) 126501
Figure 42.  Comparison of the absorbance spectra of (a) graphene, (b) silicene and (c) germanene as a function of photon energy obtained
from numerical computation. The black solid line (red dashed line) indicates that the longitudinal (transverse) gauge and gauge-invariance
of the absorbance is demonstrated here. (Reproduced with permission from [51]. Copyright (2013) by the American Physical Society.)
4.3.  Raman spectroscopy in silicene
Since buckling is an inevitable integral part of silicene, Raman
spectroscopy, a non-destructive widely adopted optical tool,
is used to explore the modification of the buckled structure in
the presence of metal clusters. Further, this method has been
shown to be an efficient tool for the characterization of vibra-
tional modes of sp2 based 2D materials [245]. Nevertheless
this method turns out to be quite sensitive towards the purity
of the layers, doping level and defects, as shown clearly in
the graphene system [246–250]. Raman spectroscopy is
based on the inelastic scattering of photons under the emis-
sion of phonons or the absorption of phonons. In the processes
under consideration, phonons with wave vector q ≠ 0 become
Raman active in the presence of defects. In fact, the defects
modify the electron–phonon coupling at various k-points of
the BZ and renormalize the electron and phonon energies.
Moreover, these defects generally break the usual selection
rules and, therefore, broadening and new peaks are manifested
in the Raman spectra. Besides, buckling distortion being IR
inactive, one needs to use Raman spectroscopy to capture
the intrinsic buckling in silicene [251]. At this junction, it is
worth pointing out that the most intense peak of graphene,
known as the G peak (E2g), occurs at 1580–1600 cm−1. Apart
from this, the other two common peaks emerge as the D peak
(1350 cm−1) and 2D peak (2700 cm−1). The G peak is due to
the bond stretching of sp2 atoms, while the D peak is related
to the breathing modes of sp2. The 2D peak is related to defect
density and does not arise from a non-defective graphene. An
additional D (A1g) peak may appear due to intervalley electron
→
defect scattering at K in the first BZ (FBZ).
An NS epitaxially grown on Ag(1 1 1) substrates turns out
to be an important avenue of research because of the evidence
of Dirac fermions along with band gap opening. However,
because of their topographic evidence of layers, it is highly
44
Review
desirable to understand the arrangements of respective bonds
in SiNSs and how these bonds affect their vibrational, as well
as electronic, properties. With these motivations, Cinquanta
et al [36] have explored the Si/Ag(1 1 1) 2D systems in terms
of a sp 2 − sp3 form of silicon with the help of Raman spectr­
oscopy, duly supported by ab initio DFT calculations. The
spectrum consists of an intense peak at 516 cm−1, present-
ing an asymmetric and broad shoulder at a lower frequency
range lying between 440–500 cm−1. This feature rules out
the full sp3 nano crystalline silicon structure. The theoretical
calculations performed in 13 × 13 − II and 4  ×  4 super-
structures have indicated a doubly degenerate E2g mode at
505 cm−1 and 495 cm−1 respectively. Within the limit of the
numerical computations, these values seem to be very close to
the experimental observation at 516 cm−1. In fact, this mode
serves as the benchmark of 2D SiNSs sp2 character in a hon-
eycomb lattice. Interestingly, in contrast to FS silicene, the
calculated Raman spectra of 2D Si superstructures also con-
sist of non-vanishing Raman intensity of several vibrational
modes, as denoted by D, T and K. A pronounced enhancement
of E2g peak intensity with excitation energy has also been
noted, indicating a typical semiconducting behavior related
to sp3 silicon. The multihybridized nature of these 2D NSs
originated solely from buckling induced distortion of the pure
sp2 hybridized structure. An additional D(A1g) may appear at
1300 cm−1 due to intervalley electron defect scattering at K in
the FBZ.
It is well known that oxygen atoms can effectively break
the symmetry in the silicene structure, resulting in a non-zero
finite band gap [252] at EF. A controllable amount of oxida-
tion thus serves as a tool in modifying the electronic states and
can be instrumental for silicene based electronic devices. Du
et al [139] have been able to establish the correlation between
the buckled structures and oxygen adatoms by STM and
Rep. Prog. Phys. 79 (2016) 126501
Figure 43.  Computed Raman spectra of hydrogenated armchair silicene nanoribbons (n)ASiNR-H (Gaussian broadening width 10 cm−1).
(Reproduced with permission from [98]. Copyright (2015) by IOP Publishing Ltd.)
Raman spectroscopy, along with help from DFT calcul­ations.
The emergence of bright protrusions in the STM images after
oxygen adatom demands in situ Raman measurements. In situ
Raman spectra for silicene oxidized under different oxygen
doses reveal the appearance of a broad shoulder [139] to the
E2g peak at lower wavenumbers (450–510 cm−1), signalling
the formation of a Si–O bond due to Si sp3 hybridization. First
principles calculations have also demonstrated that adsorp-
tion configuration and the amount of oxygen adatoms on the
silicene surface play an active role for band gap engineer-
ing under oxidation. In particular, the configuration result-
ing from oxygen atoms at bridge sites, popularly known as
double-atom-bonding overbridging O atoms (Od), seems
to give the major contribution to STM images as suggested
by the DFT calculation of superstructures of silicene layers.
Recently, various issues of Raman spectroscopy related to
sp 2 /sp3 hybridization of epitaxial silicene layers on different
Ag surfaces have been reviewed by Grazianetti et  al [253].
Raman spectroscopy thus turns out to be an important tool to
distinguish the distorted honeycomb structure in 2D materials.
DFT calculations involving buckling distortion of various
silicene clusters (e.g. Si6H6, Si14H10, etc) have indicated [251]
that the buckling frequencies of these clusters lie between
100–200 cm−1. The Raman activity of these bucking modes
can be traced back on the anisotropy related to the respec-
tive polarizabilities. The calculated G band due to the bond
stretching of all pairs of Si atoms is comparable to the exper­
imental G band of 516 cm−1 for epitaxial silicene over the Ag
(1 1 1) surface and theoretically calculated value of 570 cm−1
of low buckled FS silicene. The study has also demonstrated
that, in the presence of metal clusters, the intensity of the
Raman peaks is enhanced about 2–5 times. These enhance-
ments, however, increase with the size of the metal cluster.
45
Review
Apart from this enhancement, there occurs a red-shift of
25–30 cm−1 in the buckling frequencies of silicene fragments
due to silicene–metal cluster interaction. Besides, the presence
of the metal cluster is responsible for the appearance of new
Raman active modes which were either weaker or non-exist-
ent for the bare pristine silicene. As an example, it has been
detected in the above study that the Raman forbidden Si–Si
bending mode in the buckling distortion of Si6H6 at 99 cm−1
is allowed in the presence of Au2 and Au20 at the level of the
computation adopted for the study.
The structural and vibrational properties of silicene and
ASiNR have been explored [254] via first principles calcul­
ations. As a crosscheck, it was verified that the flat layer of
silicon atoms was unstable due to large imaginary values of
the frequencies from the phonon mode calculation around Γ
point in the BZ. In fact, the stable buckled structure of silicene
produces a non-resonant Raman peak known as a G-like peak
at a characteristic value of 575 cm−1. However, the Raman
peak of the D mode was obtained at 515 cm−1. It should be
mentioned here that the Raman G-like peak is highly sensitive
to the approximation scheme used (such as LDA or GGA) in
the exchange potential and also on the buckling parameter.
For bulk silicon, this G-like peak lies within 506–534 cm−1
while for germanene around 279–305 cm−1. The peak around
630 cm−1 in hydrogenated ASiNR with significant intensity
bears the signature of H–Si bonds. The pronounced peak
around 420 cm−1 is defect related. This theoretical study ena-
bles one to identify the atomic configuration and estimate the
width of the nanoribbons.
Further investigation of ASiNRs [249] allows for the identi-
fication of the D peak, a characteristic peak likely to be present
in defective silicene and linked to the 2D peak. The domi-
nant peak in the computed Raman spectra of hydrogenated
Rep. Prog. Phys. 79 (2016) 126501
Figure 44.  Raman spectra from 1.6 nm wide SiNRs on a Ag(1 1 0)
substrate. Top panel: exciting laser and scattered polarization are
oriented parallel to the NRs, as indicated in the inset. Lower panel:
polarizations perpendicular to NRs. Measurements are indicated
as open circles while the best fit (single Lorentzian) are indicated
by four phonon lines as full lines (blue and red lines). For clarity,
the background is subtracted in both spectra. (Reproduced with
permission from [255]. Copyright (2014) by AIP Publishing LLC.)
(n) ASiNRs (shown in figure  43) is the D peak, located in
the range 510–520 cm−1 (LDA calculations were employed).
Here n denotes the width of the nanoribbons. It is interesting
to point out that the intensity of the G-like peak is much lower
than the D one. But, for larger ASiNRs, as is the case with (16)
ASiNR illustrated in figure 43(b), the G peak is still dominant.
These calculated G-like and D peaks serve as the fingerprints
of the Raman spectra of the low-buckled structures of silicene.
Recently, SiNRs were grown [255] on the Ag(1 1 0) sur-
face in an ultra high vacuum (UHV) chamber ( p ≈ 2 × 10−10
millibars) equipped with a Si electron bombardment source
to measure in situ vibrational modes through Raman spectr­
oscopy. On these SiNRs on the Ag(1 1 0) surface, four vibra-
tional modes (shown in figure  44) at 459, 440, 266, and
202 cm−1 were identified. Besides, the narrow phonon line
widths (FWHM = 15 ± 1.4 cm−1) confirm the high uniform-
ity and periodicity of the structure. It is to be noted that the
phonon frequencies of 459 and 202 cm−1 appear only upon
excitation with polarization oriented along the NRs. This indi-
cates clearly that Raman spectra strongly depend on the ori-
entation of the sample with respect to exciting and detected
polarizations. In contrast to the report [254], the absence of
phonon peaks above 500 cm−1 in these measurements here
strongly suggests a larger deformation of the Si-NRs structure.
In recent years, the epitaxial silicene/Ag(1 1 1) system has
been explored in connection with the integration of silicene
in FET. In particular, optical techniques, along with ab initio
calcul­ations, have been invoked [256] to clarify the dramatic
46
Review
role by the supporting substrate in dictating the optical absorb-
ance of the system. The silicene/Ag(1 1 1) UV-visible spectra
turn out to be non-additive in nature and, in fact, the inter-
face states formed by the mixed Si and Ag wavefunctions play
a key role in the optical response of these low dimensional
systems. A broad bump at 480 cm−1 indicates the perturba-
tion of the D3d point with respect to (1 × 1) FS silicene by the
Ag substrate. Apart from the main peak of 4 eV, the van Hove
­singularity (vHS) occurs at the first absorption peak at 1.6 eV.
The LDA calculations have been performed for the optical
absorption spectra of the supported and unsupported (4 × 4)
supercell. For the unsupported one, the sharp interband peak
at 4 eV evolves to a broadened feature, while the vHS peak
at 1.6 eV remains in the spectra. But due to symmetry break-
ing, a band gap of 0.30 eV opens at Γ preserving the condition
A(ω ) = 0 at lower frequencies compared to the (1 × 1) super-
cell where A(ω ) = πα. The effect of the Ag substrate intro-
duces a significant change in the absorption spectra above
4 eV and a negligible contrib­ution in the visible part. The vHS
peak at 1.6 eV disappears and a red shift of the main absorp-
tion peak about 3.3 eV is seen. The observations suggest that
the bandstructure as well as the hybridization between Ag
and Si are strongly modified due to the presence of the Ag
substrate. These findings claim to play a significant impact in
other 2D elemental materials, such as germanene and stanene,
deposited on available commensurate substrates.
It is distinctly clear now that the FS silicene makes no sense
because the 2D material silicene can exist only as a material
on substrate. In this sense, DFT calculations have been fruitful
in identifying those substrates that may serve as a template for
silicene by looking carefully through the electronic coupling.
Raman spectroscopy data thus provide a remarkable assis-
tance to substrate engineering as an avenue to design silicene.
5.  Other exotic 2D materials beyond silicene
The exotic properties of silicene and germanene [257–259]
have inspired researchers to go one step ahead i.e. to search
for other startling 2D materials which are an elemental ana-
logue of graphene. As a result of this search, scientists have
theoretically predicted the existence of stanene or tinene (tin
analogue of graphene) [12, 260], phosphorene [12, 261] (gra-
phene analogue of phosphorus), arsenene, [262–264] (gra-
phene analogue of arsenic), antimonene [265], (graphene
analogue of antimony), borophene [266], (graphene analogue
of boron) and bismuthene [267], (graphene analogue of bis-
muth). These are all the cousins of graphene and silicene.
In spite of the availability of the theoretical results, the
fundamental physical properties of stanene related to the
magnetic and/or optical properties are still lacking. It has
been found [268] that the adsorption of group IV elements on
stanene disrupts the structure heavily. This disrupture occurs
at T  =  0 K as well as at elevated temperatures. Naturally, the
question arises as to whether FS stanene is stable or not. MD
simulations, however, have ensured that free standing stanene
is stable up to 400 K, and beyond this temperature, the struc-
ture is disrupted [269]. The authors have also commented that
Rep. Prog. Phys. 79 (2016) 126501
stanene grown on a substrate can attain stability and remain
stable upon the adsorption of adatoms. An optical absorp-
tion study by Mattes et al [243] reveals similar results to that
of germanene, but here, the spin–orbit splitting of the p-like
VB states at the Γ point of the BZ is 770 meV which is larg-
est among the group IV elements. Due to the large SOC in
stanene, one may expect stanene to be an ideal candidate for
TI. Xu et al [270] have indeed demonstrated it theoretically.
It has been remarked that stanene can be used as a QSH insu-
lator, having bulk gaps of a magnitude of 0.3 eV. The QSH
states can be tuned by using chemical functionalization and
by applying external strain. Modaressi et al [260] have theor­
etically explored the effect of applied strain on the electronic
properties of stanene. It has been indicated that the forma-
tion energy of stanene is 3.37 eV and 2.8 eV (per atom) in the
absence and presence of SOC, respectively. Shaidu and Akin-
Ojo have shown from first principles that Ca and Li doped
stanene leads to superconductivity [271]. However, the theor­
etical prediction of superconducting transition temperature is
considerably very low (∼0.7 K for Ca, ∼1.3 K for Li), even
lower than its bulk counterpart. DFT calculations have pre-
dicted that the properties of stanene can be tailored when it is
grown on different substrates like SrTe, PbTe, BaSe and BaTe
[272]. In the early 1990s, attempts were made to produce a
stanene-like structure [273, 274]. However, due to the non-
availability of the characterization technique at the atomic
resolution level, it was not possible to verify the formation
of a monolayer stanene structure. Recently, Zhu et  al [275]
have successfully grown monolayer stanene on a Bi2Te3(1 1 1)
substrate by using molecular beam epitaxy. Experimentally
obtained STM and ARPES data have been compared with
DFT data for electronic structure calculation. Saxena et  al
[276] have also successfully synthesized FS stanene from
few layer to mono layer. It has been predicted theoretically
that 2D stanene suffers a significant change in band gap from
0–0.45 eV by hydrogenation [311].
Unlike graphene, silicene, germanene and stanene, phos-
phorene belonging to group V is semiconducting in nature
with a direct band gap of 1.0 eV [12, 114, 261, 277]. Recently
few layer black phosphorus has been predicted to be a suitable
candidate for FETs [277–282] and the PV effect [283–285].
Similar to its bulk counterpart, it also shows a layer depend-
ent band gap transition [286]. In the case of phosphorene, it
has been predicted that hydrogen passivation gives a stable
2D sheet with a direct band gap of magnitude  ∼1 eV. Besides,
edge passivation can also tune the electronic properties [287]
of a phosphorene nanoribbon. In the case of phosphorene
through strain engineering, certain electronic properties can
be modified [288–291]. For example, the thermoelectric prop-
erties of phosphorene can be significantly enhanced by apply-
ing a suitable amount of strain [292]. These theor­etical studies
also shed light on the gas sensing properties of phosphorene.
Further studies have indicated that phosphorene possesses a
strong binding towards nitrogen-based gas molecules, por-
traying it as a viable candidate for toxic gas sensing material
[293]. Ezawa [294] explored the effect of an external elec-
tric field on phosphorene nanoribbons. The computations
have indicated the presence of a quasi-flat edge band entirely
47
Review
detached from the bulk. Through the TB model study, the ori-
gin of the flat band has been argued to be topological in nature.
By applying an external electric field, a significant change has
been observed in the quasi-flat edge band. If the electric field
is applied parallel to the ribbon, then one of the edge modes
shifts in the upward direction while the other modes shift in
the downward direction and keep their shapes unchanged.
Another group V element of current interest, lying just
below phosphorus in the periodic table, is arsenic. Kamal and
Ezawa [262] and later Zhang et  al [265] have explored the
honeycomb structure of arsenic, known as arsenene, within
the framework of DFT. They have demonstrated that both
buckled and puckered structures are stable by analyzing their
phonon spectra. Cohesive energy calculation indicates that
the buckled structure is slightly more stable than the puckered
one. Unlike graphene, silicene, germanene and arsenene pos-
sess an indirect band gap in the electronic structure. Puckered
and buckled arsenene have an indirect band-gap of 0.831 and
1.635 eV respectively. From the PDOS plot it can be seen that
near the Fermi energy, the contribution is more from the P
orbital rather than the S one, a common characteristic feature
observed in any honeycomb structure.
It is instructive to comment on some important features
of phosphorene associated with its band-structure [262]. In
the buckled structure of arsenene, the VBM is situated at the
Γ point while the CBM lies along the Γ-M direction, but in
buckled phosphorene, neither the CBM nor the VBM lies at
the k points in BZ. In puckered arsenene, the maximum of the
VB and the minimum of the CB occur along the Γ-Y direction
and at the Γ point respectively, rendering it an indirect band-
gap semiconductor, but in puckered phosphorene, the gap
occurs exactly at the Γ point. The difference between the two
VB edges near the Fermi level is small (85 meV) compared to
puckered phosphorene (500 meV).
By applying a strain of magnitude of 1% only, the puckered
system is transformed into a direct-gap semiconductor. If the
strain exceeds the limit of 6%, the gap is found to be nearly
closed. A bulk form of arsenic, known as gray arsenic, con-
sists of buckled arsenene [263, 264]. As graphene is mainly
manufactured by exfoliating graphite, likewise it is possible
to obtain arsenene by exfoliating gray arsenic.
In a similar spirit, the name of the element just below arse-
nic in the periodic table is antimony. Zhang et al [265] have
studied the honeycomb structure of antimony, which is like-
wise called antimonene. It also possesses an indirect band-
gap of 2.28 eV like arsenene. Though the bulk counterpart
of antimonene is metallic, its monolayer is semiconducting
in nature, just like arsenene. The physical properties of anti-
monene are similar to that of arsenene.
Zhang et  al [265] have indicated some physical argu-
ments to explain the puckering and electronic structure of
both arsenene and antimonene, which is distinctly different
from phosphorene. They have argued that both arsenic and
antimony have a lone pair of electrons situated alternately in
an upper and a lower plane. This arrangement of outermost
electrons is responsible for the puckering in those structures
due to PJT distortion. It has been demonstrated that from six
layers to two layers, the interlayer interaction decreases with
Rep. Prog. Phys. 79 (2016) 126501
Table 8.  Different structural parameters for puckered phosphorene, buckled arsenene, planar aluminene and bismuthene.
Phosphorene Arsenene
Lattice constant (Å) 4.53 3.60
Bond length (Å) 3.36 2.50
Buckling parameter (Å) 2.50 1.38
Energy gap (meV) 1000 2490
Effective mass (m0) 1.24 (zigzag) (Γ-K) 0.23
m0  =  free electron mass 0.16 (armchair) (Γ-M) 0.29
increasing layer thickness. It is believed that the interlayer
interaction plays an important key role in the semimetal to
wide-band-gap semiconductor transition in the arsenene/anti-
monene layered systems. When the thickness is reduced from
a layered structure to a monolayer, the CB shifts towards the
vacuum level due to quantum confinement. In arsenene and
antimonene, the bottom of the CB consists of As 4p (Sb 5p)
states coupled with small amounts of As 4s (Sb 5s) states. Six
As 4p (Sb 5p) states split into three bonding and three antibo-
nding states, opening a band gap around the Fermi level. In
silicene and germanene, the VBM and CBM consist of π type
bonding states, which are absent in arsenene and antimonene.
They have three s-bonding orbitals and a lone pair of electrons
that do not form π type bonding states. Due to these reasons,
arsenene and antimonene have different physical properties
compared to that of silicene, germanene and phosphorene.
Among the group III elements in the periodic table, Kamal
et al [295] have investigated the honeycomb structure of all
the group III elements (B-In). The investigation suggests that
the honeycomb structure of Al is most stable, known as alu-
minene. While studying the electronic properties of Li and
Na doped aluminene, they have considered four different
geometrical configurations, namely, (a) planar, (b) buckled,
(c) puckered and (d) triangular geometries. Among the four
different geometries, it has been established through phonon
spectra that the planar structure is the most stable one. Pristine
aluminene is metallic in nature due to the partial occupancies
of both σ and π bands. While analyzing the band structure,
it has been revealed that two Dirac cones appear at energies
1.618 eV and  −4.274 eV. The first cone is due to the π bonds,
which are purely made up of the pz orbital and the second one
is due to σ bonds which have a strong contribution from the s
orbital. At the Fermi energy, there appear two σ bands. Among
the two bands, one originates from mixing the px and py orbit-
als and the other is due to the s orbital. The appearance of the
Dirac point above the Fermi level is due to the incomplete
filling of σ and π bands, unlike graphene where both the orbit-
als are completely filled up. Besides, the number of valence
electrons in the outermost shell of aluminene is less than that
of graphene. Due to electron adsorption in aluminene through
Na and Li, the Fermi energy is shifted towards CB. In the
pristine system, the vHS emerges near the Fermi energy at
0.856 eV in the π band and at 0.212 eV in the σ band, but due
to Na adsorption, the vHS of the σ band appears at 0.116 eV.
Like the prediction of chiral superconductivity due to vHS at
the π band of graphene [296], one may expect this phenomena
in aluminene. Recently, Kamal et al [297] explored the elec-
tronic structure of a hybrid graphite-like structure made up of
48
Review
Aluminene Bismuthene
4.48 5.57 (planar), 4.34 (buckled)
2.59 3.05
0 0 (planar), 1.73 (buckled)
0 6 (indirect), 555 (direct)
(Γ-K) 0.20
(Γ-M) 0.24 —
BN and silicene layers. The DOS calculations have indicated
the semi-metal character of the system. More importantly, the
dispersion relation around EF is parabolic, indicating a nearly
free electron behavior similar to bulk graphite. It is important
to explore the potential of such multilayer systems as opto-
electronic devices.
It is known [266] that all bulk boron allotropes are semi-
conductors in nature and only at extreme high pressures do
they become metallic. 2D boron sheets, known as borophene,
are predicted to be metallic [298] or semimetallic [299] and
their stability is significantly enhanced by vacancy superstruc-
tures or out of plane distortions [299]. Recently, atomically
thin borophene has been synthesized [300] under UHV con-
ditions on clean silver surfaces. The STM images depict the
emergence of a planar structure with anisotropic corrugation
duly supported by first principles calculation. The electronic
band structure calculations have established that borophene
is a highly anisotropic metal. STS further confirms this
dI
metallicity of borophene through I– V curves and dV . These
observations will definitely invite further studies of metallic
borophene.
Apart from the above 2D materials arising from group
III and group IV, recently an SL of bismuth (Bi) has been
observed to possess a buckled semiconducting structure with
an indirect band gap of 500 meV [267]. This new hexagonal
2D material, known as bismuthene, is predicted to be a better
thermoelectric material in comparison to bulk Bi containing
compounds such as Bi2Te3 and BiSb [301]. In table 8 we have
summarized different structural parameters of phosphorene,
arsenene, aluminene and bismuthene. Due to the large power
factor, along with relatively lower values of κ, SL Bi exhibits
better thermoelectric performance in comparison to its bulk
counterpart. In particular, first principles calculations [267],
along with the Boltzmann theory, have been used to predict
the figure  of merit ZT values as 2.4 at 300 K and can also
be increased to 4.1 at 500 K, quite a bit larger than those
Bi-based bulk materials. It is worth pointing out that Bi con-
taining materials have been explored as TI [302–304]. Freitas
et al [305] have explored the band structure of 2D binary XBi
compounds (X  =  B, Al, Ga and In in group III elements) in a
buckled honeycomb structure under the hydrogenation pro-
cesses. The pristine bismuthene under SOC consideration
leads to an indirect band gap of 0.50 eV, while hydrogenation
can open up an indirect band gap of  ∼1 eV at the Γ point for
all the three configurations, such as top, chair-like and boat-
like. In the case of XBi heterosheets, hydrogenation can lead
to a band gap in this new class of 2D Z2 TI. The nature of
the global band (direct or indirect), as well as topological
Rep. Prog. Phys. 79 (2016) 126501
insulating properties, however, critically depend on the X ele-
ment, spatial configuration and applied strain. Hydrogenation
thus turns out to be a simple chemical route to preserve the
band topology of the pristine XBi phases. It will be interest-
ing to explore the magnetic and optical properties of this new
class of TI materials.
The advantage of silicene is that it can be easily interfaced
with the modern Si based industry. Several approaches have
been proposed to design novel nano-structures for device
application. One of the viable routes is to combine C and Si to
make various nano-structures. As a result, Si and C atom com-
bined nanotubes [306, 307] and Si–C nanowires [308] have
been predicted. These nano-structures have been found to be a
promising candidate for hydrogen storage. Theoretically pre-
dicted Si–C zigzag nanoribbons [309] have been noticed to
be half-metallic without the assistance of any external electric
field [310]. Si–C nanorods have been experimentally real-
ized through a reaction between carbon nanotubes and SiO
[310]. Ciraci et al [34] have studied the stability of Si–C NS
by employing DFT calculation. It has been reported from their
study that Si–C NS is semiconducting in nature, unlike pris-
tine graphene and silicene. Drissi et  al [311] have explored
the hydrogenation effect of this hybrid system by using DFT.
It has been revealed from their work that the full hydrogena-
tion increases the band gap (∼1.0 eV). Drissi et al [312] have
also studied the electronic and optical properties by incorpo-
rating the many-body effect. Motivated by the above exotic
features, we have recently studied the electronic and magnetic
properties of this hybrid system [313] by introducing disorder
through DFT. Here the system has been made disordered by
substitutional doping and also by creating a single vacancy.
B, Al, N and P have been chosen as dopant atoms in these
hybrid structures. From our magnetic property study, it has
been found that the Si vacancy structure possesses the highest
magnetic moment of the order of 4 µ B. One of the key obser-
vations in these hybrid structures is that magnetism can be
induced via midgap states. It has been observed that the band
gaps vary between 1.43–2.38 eV and 1.58–2.50 eV for spin-up
and spin-down channels, respectively.
6.  Conclusions and future directions
In this theoretical review, we have attempted to cover some
important contributions of the electronic, magnetic, and opti-
cal properties (including Raman spectroscopy) of silicene,
one of graphene’s cousins in the 2D world. The tunability of
the material properties in such elemental silicene sheets and
disks (edge related) or nanoribbons offers a novel prospect of
engineering discrete applications. Theoretical DFTB calcul­
ations have been shown to indicate an appropriate direction
to these silicene derivatives. We have also included the theor­
etical predictions of the magnetic and optical properties of
chemical functionalized silicene (both in monolayer as well
as in bilayer). A vertical electric field can also be effective in
controlling the electronic band structure of various silicene
derivatives. Defects can also significantly modify the struc-
tural, electronic and optical properties of vacancy modulated
49
Review
silicene. Some of the interesting features related to the sym-
metry of a TB Hamiltonian have been deliberated. This will
enable one to understand some of the intriguing features
associated with the band structure and related optical trans­
itions in various derivatives of silicene. These features related
to symmetry will help one to understand the underlying phys-
ics of topological phase transition and zero modes in silicene.
A comparison with the graphene counterpart has been incor-
porated to indicate the importance of the results obtained in
theoretical calculations. Unlike graphene, silicene cannot
grow in FS form and for its growth, a suitable single metal
substrate is required. However, for device fabrication, instead
of the metallic substrates, non-metallic/insulating substrates
are necessary. The importance of a universal feature of opti-
cal absorption in this material has been connected with the
Ag substrate. Moreover, the theoretical study with various
substrates will trigger research in experimental observations
in connection with electronic band structures and DOS. In
this situation, the growth of silicene with good lattice match-
ing on large silicon wafers via buffer layers may provide an
alternative way to integrate silicene nanoscale devices on a
silicon platform. These large silicon wafers via buffer lay-
ers are also found to be very important for using silicene
as an FET. Thus, it is expected that advances in synthesis
techniques for producing a hetero bilayer or multilayers of
silicene will be a significant milestone towards exploring
their tremendous potential for the development of next gen-
eration nanoelectronics devices. DFT calculations along with
Raman studies will be instrumental for identifying the appro-
priate substrate and other relevant parameters for the growth
of silicene on substrates. The unique unconventional features
besides silicene associated with other innovative 2D struc-
tures such as germanane, phosphorene, arsenene, stanene,
aluminene, borophene and bismuthene have been discussed
and these structures are expected to play an important role in
overcoming some of the constraints in nanodevices. Although
some preliminary studies, both in theory and synthesis pro-
cesses, have been pursued, it is necessary to explore some
modifications of their electronic band structure and optical
properties in the presence of the combinations of strains, dop-
ing and defects. Armed with the theoretical predictions from
DFTB, we strongly feel that there are unexpected properties
of various structures made from silicene. These systems will
also expand the horizon of our understanding of the underly-
ing physics, which may lead to some strange unanticipated
phenomenon.
After acceptance of this review article, we came to know
another interesting review article on silicene which mainly
discusses the recent experimental successes of silicene and its
various potential applications in nanoelectronics. Zhao et al
[314].
Acknowledgments
This work is partially supported by DST-FIST, DST-PURSE,
the Government of India. One of the authors (SC) gratefully
acknowledges DST, the Government of India for providing
Rep. Prog. Phys. 79 (2016) 126501
financial assistance through DST-INSPIRE Fellowship
(IF120579) scheme. We want to thank Dr Palash Nath for
critical reading of the manuscript. The authors would also like
to thank the reviewers and the associate editors for their criti-
cal comments and suggestions to improve the quality of the
manuscript.
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