Recent Development in 2D Materials Beyond Graphene

Progress in Materials Science 73 (2015) 44–126
Contents lists available at ScienceDirect
Progress in Materials Science

journal homepage: www.elsevier.com/locate/pmatsci
Recent development in 2D materials beyond

graphene
Ankur Gupta a,b,c,1, Tamilselvan Sakthivel a,b,c,1, Sudipta Seal a,b,c,d,⇑
a
Advanced Materials Processing and Analysis Center, University of Central Florida, Orlando, FL 32816, USA
b
Nanoscience Technology Center, University of Central Florida, Orlando, FL 32816, USA
c
Department of Materials Science and Engineering, University of Central Florida, Orlando, FL 32816, USA
d
College of Medicine, University of Central Florida, Orlando, FL 32816, USA
a r t i c l e i n f o a b s t r a c t
Article history: Discovery of graphene and its astonishing properties have given birth
Received 16 January 2014 to a new class of materials known as ‘‘2D materials’’. Motivated by
Received in revised form 18 February 2015 the success of graphene, alternative layered and non-layered 2D
Accepted 24 February 2015
materials have become the focus of intense research due to their
Available online 14 March 2015
unique physical and chemical properties. Origin of these properties
ascribed to the dimensionality effect and modulation in their band
Keywords:
Materials beyond graphene
structure. This review highlights the recent progress of the state-
2D layers importance/uniqueness of-the-art research on synthesis, characterization and isolation of
TMD layers single and few layer nanosheets and their assembly. Electronic, mag-
h-BN netic, optical and mechanical properties of 2D materials have also
Silicene and germanene been reviewed for their emerging applications in the area of catalysis,
Oxides and hydroxides electronic, optoelectronic and spintronic devices; sensors, high per-
Group IV and III-V elements formance electrodes and nanocomposites. Finally this review con-
Kaolinite
cludes with a future prospective to guide this fast evolving class of
2D materials in next generation materials science.
Ó 2015 Published by Elsevier Ltd.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2. Classification of materials based on dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
⇑ Corresponding author at: Advanced Materials Processing and Analysis Center, University of Central Florida, Orlando, FL
32816, USA. Tel.: +1 4075928565.
E-mail address: [email protected] (S. Seal).
1
Ankur Gupta and Tamilselvan Sakthivel have contributed equally in this review article.
http://dx.doi.org/10.1016/j.pmatsci.2015.02.002
0079-6425/Ó 2015 Published by Elsevier Ltd.
A. Gupta et al. / Progress in Materials Science 73 (2015) 44–126 45
2.1. Zero dimensional (0D) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

2.2. One dimensional (1D) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3. Two dimensional (2D). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.4. Three dimensional (3D) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3. Importance/uniqueness of 2D materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4. Classification of 2D materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.1. Layered van der Waals solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2. Layered ionic solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3. Surface assisted nonlayered solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
5. Synthesis methods for 2D materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.1. Micromechanical exfoliation using scotch tape. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.2. Liquid exfoliation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5.3. Chemical vapor deposition (CVD). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.4. Van der Waal epitaxial growth on substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.5. Hydrothermal synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6. Characterization methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.1. Microscopy techniques for 2D materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.1.1. Atomic force microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.1.2. Ultrasonic force microscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
6.1.3. Electron microscopy techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.2. Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6.3. Photoluminescence (PL) spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.4. X-ray diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
6.5. Characterization possibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7. Nanomechanics of 2D layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.1. Mechanical properties of 2D materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2. Bulge test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3. Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7.4. Contact adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7.5. Blister test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7.6. Van der Waals force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8. 2D materials, their properties, and application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8.1. TMD layers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8.1.1. Synthesis of TMD layers (MoS2 and WS2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
8.1.2. Physical properties of MoS2 and WS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
8.1.3. Functionalization of TMDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
8.1.4. Applications of MoS2 and WS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
8.2. Hexagonal Boron Nitride (h-BN). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
8.2.1. Synthesis of BN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8.2.2. Physical properties of BNNS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8.2.3. Wide band gap modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
8.2.4. Thermal conductivity of BNNS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.2.5. Mechanical property of BNNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.2.6. Functionalization of BNNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.2.7. Application of h-BN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.3. Silicene and germanene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
8.3.1. Structural and electronic properties of silicene and germanene . . . . . . . . . . . . . . . . . . . 89
8.3.2. Functionalized silicene and germanene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
8.3.3. Strain induced effect in Si and Ge monolayer and their functionalized derivative . . . . 95
8.4. 2D layered oxide and hydroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.4.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.4.2. Assembly of 2D nanosheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
8.4.3. Electronic properties and application in electronic devices . . . . . . . . . . . . . . . . . . . . . . 100
8.4.4. Catalytic and luminescent properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8.4.5. Magnetic properties and application in spin-electronic devices . . . . . . . . . . . . . . . . . . 102
8.5. Graphene analogue binary compound of group IV and III–V elements . . . . . . . . . . . . . . . . . . . . 104
8.6. Kaolinite (aluminosilicate, Al2Si2O5(OH)4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.6.1. Physicochemical properties of Kaolinite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.6.2. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
46 A. Gupta et al. / Progress in Materials Science 73 (2015) 44–126
9. Future prospects and concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Acronyms
0D zero-dimensional
1D one-dimensional
2D two-dimensional
3D three-dimensional
AFM atomic force microscope
ARPES angle-resolved photoelectron spectroscopy
B–C–N boroncarbon–nitrogen
BNNS boron nitride nanosheets
BNNT boron nitride nanotubes
CBM conduction band minimum
c-BN cubic boron nitride
CVD chemical vapor deposition
CMOS complementary metal oxide semiconductor
CNT carbon nanotube
DBs dangling bonds
DFT density functional theory
DGU density gradient ultracentrifugation
DL-Si double-layer silicene
DMF dimethylformamide
DOS density of states
EELS electron energy loss spectroscopy
FETs field-effect transistors
FQM fluorescence quenching microscopy
FRET fluorescence resonance energy transfer
GO graphene oxide
h-BN hexagonal boron nitride
GGA generalized gradient approximation
HB high buckled
HOPG highly oriented pyrolytic graphite
HMDS hexamethyldisilazane
HRTEM high resolution transmission electron microscopy
IR infrared
k thermal conductivity
LB Langmuir–Blodgett
LBL layer-by-layer
LDA local density approximation
LDH layered double hydroxide
LEDs light emitting diodes
LEED low-energy electron-diffraction
LEEM low-energy electron microscopy
MD molecular dynamics
MBE molecular beam epitaxy
MOSFET metal–oxide–semiconductor field-effect transistor
MSA methanesulfonic acid
MX2 metal atoms (M) and chalcogen atoms (X)
NEMS nanoelectromechanical systems
NFC nanofibrillated cellulose

NSM nanostructured materials
ODA octadecylamine
PAW projector augmented wave
PEG polyethylene glycol
PFM piezoelectric force microscopy
PL photoluminescence
PMMA poly(methyl methacrylate)
PZC point of zero charge
QSHE quantum spin hall effect
REELS reflection electron energy eoss spectroscopy
SAED selected area electron diffraction
SAXS small-angle X-ray scattering
SEM scanning electron microscopy
SiNT silicon nanotubes
SOC spin–orbit coupling
SiC silicon carbide
STEM scanning transmission electron microscopy
STM scanning tunneling microscopy
TB tight-binding
TEM transmission electron microscopy
TERS tip-enhanced raman spectroscopy
TEM-EDS transmission electron microscopy-based energy dispersive spectroscopic
TMA tetramethylammonium
THF tetrahydrofuran
THz terahertz
TMDs transition metal dichalcogenides
UFM ultrasonic force microscopy
UHV ultrahigh vacuum
UV ultraviolet
VASP Vienna Ab initio simulation package
VBM valence band maximum
XRD X-ray diffraction
XPS X-ray photoelectron spectroscopy
1. Introduction
In human history, the collecting of scientific information and technology seem like to have evolved
in a slightly exponential, self-enhancing manner. The frequency of technological revolutions has
increased from the previous centuries and will probably increase at a greater extent throughout the
21st century and onwards, universal properties permitting. Now, we are at the foundation of addi-
tional scientific and technological revolution called the age of nanotechnology. The potential of this
technology ensures us to manipulate materials at the nanometer scale, resulting in tools and technolo-
gies never visualized earlier, from nanoparticle based cancer therapy [1] to high performance compos-
ites [2–4], and thus, nanotechnology opens up new frontiers for innovation in medicine, electronics,
materials, etc. [5,6]. In addition to the rise of new technologies, a novel class of low dimensional sys-
tems distinguishes the development of nanoscale sciences. For example, the zero-dimensional (0D)
class of quantum dots, one-dimensional (1D) class of nanoribbons, nanotubes, and nanowires, two-
dimensional (2D) class of single-atom thick materials, and three-dimensional (3D) class of nanoballs
and nanocones [7]. A main feature that differentiates several categories of nanostructure is their
dimensionality. Dimensionality is one of the most fundamental material parameters, which not only
defines the atomic structure of the material, but also determines the properties to a significant degree
[8]. The same chemical element or compound can exhibit different properties in different dimensions.
Carbon nanostructures are a leading material in the nanotechnology field. The discovery and
research of carbon materials has considerably contributed to the advancement of modern day science
and technology. After the discovery of fullerene and single walled carbon nanotube (CNT), which are
zero-dimensional and one-dimensional carbon nanomaterials respectively, the researchers have tried
to isolate 2D graphitic material or to make 1D nano-ribbons from 2D crystals. The efforts have started
to pay off since 2004 with the first isolation and electrical characterization of graphene transistor
reported by Geim and Novoselov [11]. Most of these nanostructures are compiled exclusively of sp2
hybridized carbon atoms establishing several structures, from the soccer ball like fullerene (C60) to
the single atom thick plane of carbon called graphene, to the ‘‘rolled up’’, tubular sheets of graphene:
carbon nanotubes as shown in Fig. 1 [9–12]. The physicochemical properties of these graphene like
structures, even though their being composed of sp2 carbon, are as different as their atomic structure.
From the earliest theoretical investigation into the electronic properties of graphene and graphite, it
has become clearer that graphite has some unusual properties [13]. Later, many more properties of
graphite, graphene and CNT have come to light, for example the high charge carrier mobility of gra-
phene and CNT [4,14–16].
Physicochemical properties and applications of graphene based materials and reduced graphene
oxide had been reported earlier [17–20]. After the discovery of graphene, many researchers would
not realize that more than a dozen 2D materials can be isolated and studied in less than 10 years.
Progress in graphene research had a spillover effect by way of leading to an interest in other 2D
materials like for example metal nitrides and carbides. 2D nanostructures are one of the greatest
widely studied materials because of the unique physical singularities that happen when heat transport
and charge is confirmed to a plane. Due to the unique properties, 2D nanostructures are anticipated to
have an important influence on a huge diversity of applications, extending from high performance
sensors, electronics to gas separation or storage, catalysis, inert coatings and support membranes,
etc. Right now, the 2D materials family includes not just carbon material but also transition metal
dichalcogenides (TMDs), and layered metal oxides. One of the most promising applications of 2D
materials is in electronic devices [21,22]. With respect to the electrical properties, one can fabricate
a new generation of superconductors, metallic materials, semimetals, semiconductors, insulators from
the 2D materials.
Even though graphene is the last one to be isolated in the carbon materials family, it serves as the
building block for other family members with different dimensionalities. In particular, single layers of
TMDs have attracted notable attention because of their diverse properties and natural abundance.
Despite the similarity in the chemical formula, MX2, where typically M is transition metal of groups
4–10 (typically Mo, Nb, W, Ni, V, or Re) [23,24] and X is a chalcogen (typically Se, Te, or S) [25–27].
While the bonding of the tri-layers are covalent, neighboring sheets are bonded via Van der Waals
interactions to grow 3D crystals. There are currently 40 different types of combination of TMDs with
different chalcogen atoms. Based on the co-ordination and oxidation state of the metal atoms, TMDs
ranging from insulators such as HfS2, semiconductors such as MoS2, semimetal such as TiSe2, to true
metals such asNbSe2, which can even exhibit superconductivity at low temperature [28–30]. Besides,
a solid attention in group-IV 2D oxides has newly developed. These different types of nanosheets
whether oxides or TMDs, have been studied experimentally or computationally to understand their
electronic structure and compared with graphene [31].
Table 1 lists all the current members in the 2D layered materials family [32]. However, stability is a
critical issue. The blue shaded materials are constant under ambient environments (room temperature
in air) for monolayers. Perhaps green shaded materials are stable in air, but those may be steady only
in inert atmosphere are shaded pink. Gray shading means monolayer has been exfoliated, but no fur-
ther information has yet been provided other than atomic force microscope (AFM). Still, there is a
complete periodic table of crystalline materials individually having various properties such as
mechanical, transport and electronic properties, and the probability to make single- or several-atom
polyhedral dense 2D sheets from any material remains. Furthermore, this layered 2D materials exhi-
bits a combination of excellent electronic [33], mechanical [34], optical [35], and thermal properties
[36], which may substitute silicon in electronics, photonics, and nanoelectromechanical system
(NEMS) as well in this century or next. This is most researchers dream about 2D materials into real
life applications.
Fig. 1. (a) A C60 fullerene molecule, a carbon nanotube and graphite are in the order from left to right. Graphene, a single sheet
of graphite, can be considered as building block of all these carbon structure (image produced from Ref. [9]). (b) Honey-comb
lattice structure. (c) Dark shiny appearance of graphene. B and C images produced from Ref. [10]).
Table 1
2D materials family (table produced from Ref. [28]).
2D materials in nano and micro form with 1D restricted that are in close contact with each other to
form boundaries. 2D nanosheets and quantum features in their optical and electronic properties can
be prepared both uniform and equivalent in thickness and size by several approaches presently used
in material synthesis. It was not until 2004 that physicists were able to first isolate individual gra-
phene planes using adhesive tape to obtain flakes that exhibited unique electronic properties [37].
The discovery has led to a great interest in the science community to study the large scale production
of 2D materials. Van der Waals materials can be chemically and mechanically exfoliated into single or
few layers which was shown in the last decade [32]. This preliminary work has motivated many
researchers to obtain and distinguish these layers to unveil new properties. In the field of graphene
research, several methods are reported for preparing, detecting, transferring, characterizing and con-
trolling the properties of 2D layered materials [8,31]. Additionally, new synthetic techniques including
solvothermal, solution based and epitaxial methodologies have allowed the possible ways to produce
new single- or few layers and van der Waals materials. These well-known techniques have allowed
the field of 2D materials beyond graphene to establish rapidly. Soon after these discoveries, many gra-
phene’s ‘‘cousins’’ had been suggested that 2D nanosheets of groups IV and II–VI elements, such as sil-
icene [38,39] and germanene [40,41] might demonstrate similar properties as graphene. In addition,
these 2D semiconductor materials are very useful structural agents that can be modified and com-
bined into composites for an extensive application.
There are many layered materials with strong in-plane chemical bonds and weak coupling between
layers. These layered structures provide the opportunity to be cleaved into individual freestanding
atomic layers. When the thickness of layered material is reduced to single or only few layers, some
extraordinary variations occur in their electronic properties. The research of graphene established a
model of methods to study 2D materials not only experimentally in synthesizing, transferring and
characterizing, but also theoretically in electronic structure, quantum Hall effect and spintronics.
Due to their symmetry, and high porosity, nanofilms coated with thin layers of inorganic graphene-
like materials have potential applications from ultralight anti-corrosive materials to electron field
emitters [42,43]. In addition, the semiconducting properties make the inorganic nanofilms potential
materials for further miniaturization of optoelectronic materials. Finally, the hexagonal structure of
graphene-like material make them possible applications in nonlinear optics and solar technology
because these conducting nanofilms can detect self-inductance and resistance quickly and efficiently.
For example, applications range from the sharp tips on scanning spectroscopy probes to other mag-
netic, electronic detecting devices [44–46]. With the discovery of many more of their exotic proper-
ties, the incentive for further research and the promise of practical applications of these materials
became greater.
Identifying the uniqueness/individuality of the 2D nanostructure, people may think that these lay-
ered materials will expose novel and unpredicted properties allowing many innovative openings. This
present review article aims to deliberate the highest degree of development of graphene like materi-
als. First, we will elaborate the importance and uniqueness of 2D materials followed by the classifica-
tion of 2D materials to know about van der Waals and ionic solid layers. We also discuss the several
approaches to prepare and few-layer 2D materials for many applications and an experimental guide
for recognizing and describing mono- or few- layer thick materials, besides outline the basic principle
and importance of emerging techniques that gives overall information about the materials. Further,
this article describes the various methods to understand the nanomechanics of 2D materials
system. Finally, we explained many different newly developed 2D materials, their properties and
rewards of mono-, few-, and many layers in field-effect transistors, valley-tronics, and many other
applications.
2. Classification of materials based on dimension
What is nanostructured material (NSM)? Why NSMs are more attractive? Does the properties of
NSMs varies with dimension? How to define nanocrystals? In the past decade, the interest in
Nanostructured materials (NSMs) had an enormous impact and industrial potential deriving from
the fact that new properties are acquired at nanoscale and also these properties change with their size
or shape. NSMs are defined as a solid material characterized by at least one dimension in the nanome-
ter range. Size effects establish an exceptional and intriguing aspect of nanomaterials. The effects
determined by the size are part of the evolution of physicochemical features of these restricted sys-
tems with changing size. The properties of a material are identified by a specific length scale, com-
monly at the nanometer dimension. A crystalline material having at least one dimension smaller
than 100 nm is said to be a nanomaterial. A nanocrystal smaller than the exciton Bohr radius for that
material, in at least one dimension, is said to be quantum confined. A nanomaterial, can be nano-sized
along only one, two or all the three dimension, in the form of a film, rod, or a dot. There is several
terminology, to ascribe dimensionality to nanomaterials, and confusion arises because some describe
the number of dimensions of confinement (or nano-scale size) which is different from bulk materials.
Gleiter was the first one who gave the early classification of NSMs [47] and was further described by
Skorokhod [48]. However, this arrangement was not completely deliberated because of low dimen-
sional structures such as nanotubes, fullerenes, and nanoflakes, which were not considered at that
time. Therefore, a modified classification scheme had been reported [49], in which all low dimensional
NSMs such as 0D, 1D, 2D and 3D are comprised.
2.1. Zero dimensional (0D)
The density of states of quantum-confined nanocrystals has characteristic shapes for different
dimension nanomaterials and the differences are due to the degree of confinement of the electrons.
For 0D NSMs, the excited electrons are completely confined in all the three dimensions and they
behave analogous to atomic/molecular clusters with discreet states that are well separated in energy.
In the mid-19th century, Michael Faraday performed the first modern scientific experiments with
nanomaterials, and determined the particulate nature and size dependent optical properties of col-
loidal gold [55]. There has been more interest in the fabrication of 0D nanomaterials by chemical
and physical methods with well-ordered dimensions. In the recent years, 0D NSMs such as heteroge-
neous particle arrays, uniform particles array (quantum dots), hollow spheres, onions, nanolenses, and
core–shell quantum dots have been produced by many research groups [50–54,56–59]. Different
types of 0D NSMs images are shown in Fig. 2. Furthermore, 0D quantum dots has been widely consid-
ered in solar cells [60], light emitting diodes (LEDs) [61], lasers [62], and single-electron transistors
[63]. The pregnancy test-kits (gold nanoparticles), antibacterial bandages (silver nanoparticles), sev-
eral formulations of sun-screen lotions (SiO2 nanoparticles, or other oxide ceramic nanoparticles)
are example of consumer products that involves chemically synthesized OD NSMs. The 2014 Nobel
Prize for blue LED’s in Physics recently acknowledged the profound novelty of the physical properties
that can be observed in NSMs.
2.2. One dimensional (1D)
1D nanomaterial has nano-scale sizes along two dimensions and having a rod or wire-like appear-
ance. In such nanomaterials, quantum confinement and surface area related nanoscale effects are
more pronounced compared to 2D nanomaterials, while at the same time they can be integrated
and/or connected into device architectures due to single bulk-like dimension that is absent in 0D
nanomaterials. In the previous decade, interest in 1D materials have increased because of their impor-
tance in an extensive range of potential applications. In addition, they are anticipated to play a signifi-
cant role in fabricating EEDs, optoelectronic, and electronic in nanoscale dimensions. 1D
nanostructured materials such as nanowire, nanotubes has reached a substantial consideration after
the groundbreaking work [64]. Due to differences in quantum mechanical parameters of electron
and phonon transport [65], it has been theoretically shown that nanowires of certain alloys can be
made to have good electronic conduction with decreased thermal conduction [66], showing good
potential for high performance thermoelectric materials [67]. Some microscope photographs of nanor-
ods, nanowires, nanoribbons, nanobelts, nanotubes, and hierarchical nanostructures are shown in
Fig. 3 [68–77].
2.3. Two dimensional (2D)
There are many layered materials with strong in-plane chemical bonds and weak coupling between
the layers. These layered structures provide the opportunity to be cleaved into individual freestanding
atomic layers. These layers with one dimension strictly restricted to a single layer are called
two-dimensional (2D) material. The density of states for 2D materials, exhibits a quasi-continuous
step-like increase with increasing excitation energy [78]. These changes in the density of states for
Fig. 2. Electron microscope image of various 0D NSMs synthesized by several research groups. (a) Quantum dots [50], (b)
nanoparticles binary arrays [51], (c) hollow core–shell nanoparticles [52], (d) hollow sphere [53], and (e) hollow MoS2
nanospheres [54]. Reprinted by permission of ACS Publishers.
Fig. 3. Electron microscope image of various 1D NSMs, prepared by several research groups. (a) Nanowires [72], (b) nanorods
[73], (c) nanotubes [74], (d) nanobelts [75], (e) nanoribbons [76], and (f) hierarchical nanostructures [77]. Reprinted by
permission of ACS Publishers.
exciting electrons alters the way excitation energy interacts with the valence electrons, thus changing
the fundamental properties with size as well as shape in quantum confined nanomaterials. Currently,
fabrication of 2D materials (including quantum wells) have become an important field in current
materials research because of the physicochemical characteristics that are dissimilar from the bulk
counterpart. Mainly, these materials with definite geometries show exclusive shape-dependent fea-
tures and successful application in nanoelectronics devices [79,80]. Other interesting features of a
Fig. 4. Electron microscope image of different types of 2D NSMs. (a) Nano island structure [85], (b) branched nanostructures
[86], (C) nanoplates [87], (D) nanosheets [88], (E) nanowalls [89], and (F) nanodisks [90]. Reprinted by permission of ACS
Publishers.
2D material is not only for basic understating of growth mechanism, but also for developing innova-
tive applications in photocatalysts, sensors, nanoreactors, and nanocontainers, [81]. Important 2D
nanostructure images are shown in Fig. 4, such as island structure (junctions), nanoplates, nanodisks,
branched structures, nanoprisms, nanosheets, and nanowalls [82–90].
2.4. Three dimensional (3D)
3D nanostructures have concerned significant attention in the recent years due to high sur-
face area and physicochemical properties when compared to their bulk materials due to quan-
tum size effects [96,97]. It is long-familiar that the performances of these materials, mainly
depend on the shape, size, morphologies, and dimensionality, which are considered to be an
important role in their quality execution and applications. Thus, many researchers show their
interest in preparing 3D materials with a uniform and well-ordered structure and morphology.
Additionally, these well-ordered and innovative 3D NSMs are used in many different applications
such as electrode materials for batteries, catalysis, and magnetic material [98–100]. Furthermore,
higher surface area and high absorption capacity of 3D NSMs have attracted rigorous research
interest recently [101]. Then again, such highly porous materials with 3D could extend to a
superior conveyance of the molecules for catalytic applications [101–103]. Microscope images
of typical 3D NSMs are shown in Fig. 5. (nanopillers, nanoballs, nanocones, nanocoils, and nano-
flower) [91–95].
3. Importance/uniqueness of 2D materials
One may ask several questions about 2D materials. What is the uniqueness of 2D materials? Why it
is more attractive? Why the properties of 2D materials are dissimilar from its bulk structure? Does 2D
NSM have a chance to become the next disruptive technology? As we know that, 2D inorganic materi-
als have received great interest recently, because of their particular physical properties due to the
quantum size effect, which is related to their nanosized thickness. Some remarkable changes occur
in electronic and optical properties of layered materials, which may be due to the electron confine-
ment and also the layers are in close contact with each other to form interfaces. This absence of
Fig. 5. Electron microscope image of different types of 3D NSMs, (a) nanocones [91], (b) nanoballs [92], (c) nanopillers [93], (d)
nanocoils [94], (e) nanoflowers [95]. Reprinted by permission of ACS Publishers.
interlayer interaction is very important in finding their band structure. Chemical and mechanical
response also plays an important role in changing their properties because of quantum effects and
high surface to volume ratio.
Are the properties of 2D materials so unique to overshadow the unavoidable inconveniences
of switching to a new technology? The advancing R&D activity on 2D materials has already
shown a phenomenal development aimed at making 2D materials suitable for industrial applica-
tions. The production of 2D materials is one striking example of the rapid development toward
commercialization, with progress from random generation of micro to large-scale flakes in
the laboratory [80], roll-to roll processing of nanosheets of a size approaching the meter-scale
[104].
2D materials are an ideal candidate for engineering a new class of materials, and many examples
have already been realized in practice. Indeed, ‘‘all-surface’’ nature of 2D materials offers the oppor-
tunity to tailor its properties by surface treatments (e.g. by chemical functionalization [105]). In addi-
tion, 2D materials can be easily obtained in the form of a dispersion of small nanoflakes [106]. These
retain many of its outstanding properties, and can be used in well-established approaches for the
realization of composite materials with improved performance [107,108].
One of the reasons for the fast progress of 2D NSMs research is the multitude of unique properties
observed. Being just one atom thick, 2D materials immediately appears as the most suitable candidate
to eventually create a new generation of electronic devices. Because these materials include its 2D nat-
ure, enabling easy processing and direct access to the mobile charge carriers, chiral properties of
charge carriers, a very high carrier mobility – both at room and low temperature, and high thermal
conductivity. 2D crystals have two well-established allotropes, single layer, where charge carriers
resemble relativistic Dirac particles [109], and few layers where electrons also have some Dirac-like
properties, but have parabolic dispersion [109]. In many cases, both allotropes are gapless semicon-
ductors. However, unlike the single layer, where the absence of a gap is protected by the high symme-
try of the honeycomb lattice, few layers are more versatile: a transverse electric field can open a gap
[110–112] and its low-energy band structure can be qualitatively changed by relatively weak strain
[113]. This speculative performance of the electrons makes very attractive to study relativistic effects
of 2D materials in condensed matter research. Understanding the transport properties of 2D materials
also includes its behavior in the presence of a strong – quantizing – magnetic field. This behavior is the
display of the fundamental phenomenon of quantum Hall effect [11,114], which consists in the precise
quantization of the Hall resistance of the device. This strange band structure is improved to a common
one once more layers (more than three) are stacked.
In addition, at a particular point both the valence band and conduction band touch each other in 2D
materials [115], offering only certain electronic state near the Fermi level thus these materials called
zero gap semiconductor or semimetal. The band structure of 2D NSMs is highly sensitive to any
change because of their brittleness in single point contact such as mechanical deformations, external
electric fields, doping and adsorbents, which is necessary for sensor applications. This is similarly dis-
cussed an ambipolar part onto 2D NSMs, i.e. charge carrier contains either electrons or holes depend-
ing on dopant material [37]. But, doping is not continually necessary to alter the charge carrier, local
electric fields can also modify the charge carrier sign. This peculiar property of 2D material plays an
important role in creating p–n junction transistors with high mobility and this is the base of existing
complementary metal oxide semiconductor (CMOS) technology.
Structural analysis of 2D NSMs also proves that it can exhibit good quality crystals in few micron
scales [116]. The defect free materials make the electrons move freely without scattering, even on
rough substrates. The absence of scattering exhibits in large mobilities [14] of the charge carrier
and displays the fundamental phenomenon of quantum Hall effect, even at both room temperature
and low temperature [117]. Additionally, a direct band gap single layer 2D materials are used in
FETs [118], on/off ratios of 108 have been achieved. It has excellent electrostatic integrity that allows
sub-nanometer thickness, flexible electronics, and may have 100,000 times less power consumption in
standby state than traditional Si transistors [118].
2D materials are excellent candidates for high-gain photo-detection because the charge carriers in
these materials show large mobility. Thus, conductivity of this material is highly sensitive to electro-
static perturbation via photogenerated carriers adjacent to the top layer (surface). This makes 2D
materials a predominantly auspicious material for extraordinary gain photo-detection by employing
the photo-gating effect. Therefore, the demonstration of photo-detection improvement with the 2D
material would be the foundation for a plethora of applications including biomedical imaging, inte-
grated optoelectronic devices, quantum information technology remote sensing, and optical commu-
nications. Additionally, the thickness of 2D materials gives admittance to field effects observations in
the sample conductance, which is important for application in sensors and optoelectronics. In addi-
tion, the electron waves of 2D materials are accessible to complete surface characterization techniques
because of one atom thick [111].
The 2D material’s electronic band structures are equally interesting. The zero band gap of these
materials allows the large range of light absorption in the possible electromagnetic spectrum, extend-
ing from the infrared (IR) to the ultraviolet (UV) [119]. This opens up a huge number of options of elec-
tronic transition resulting in high performance optoelectronic devices and other basic essential studies
related to optics and photonics [120]. Simultaneously, a few layers of 2D material present absorbance
of less than 10% and in single layered material, it is 2.3%, which may be due to their thickness and
transparency [121]. This extraordinary opaque property joined together with their excellent conduc-
tivity makes them highly applicable as transparent electrodes in many electronic devices, including
solar cell and liquid crystal devices [122,123]. Even though this is definitely a fascinating issue, the
optical properties of these materials are possibly unfamiliar and the relationship between optical
and electrical properties will bring new fields into 2D materials research.
Practical implementation of 2D materials requires an understanding of its performance in real
devices, as well as its durability under ambient and extreme conditions. A specialized effort will be
needed to study the reliability of 2D materials based devices, such as electric or thermal stress test,
device lifetime, etc. To preserve device performance, it is likely that some protection of the 2D material
and the metals will be needed to minimize the environmental effects.
2D materials are extremely very strong as graphene ever tested. It gives an extraordinary breaking
strength [124], compare to steel it is 200 times higher and also these materials are unpredictably flexi-
ble. This makes the 2D material a desirable addition to lightweight polymer, and the enforcer of their
mechanical properties. Moreover, as ultrathin stretchable membrane, single layer is an ideal material
for the nonlinear tuneable electrochemical systems. It can withstand more than 20% elastic distortion
and also presents extraordinary large flexibility. Creases and pleats are quite frequently identified
without the requirement for rupture [116]. Since it is very thin and breaks like glass at larger strain,
these materials are considered to be brittle. In summary, 2D nature together with its chemical bond
strength also makes an interesting material from a mechanical standpoint. Chemical modification of
2D materials is also important. In this aspect, it has been shown that functionalization of 2D material
can make a metal to insulator conversion [125], chemical doping can be formed with various metal
ions [126]. With the presence of defects or functional groups, mechanical properties can be tuned
[127]. These chemical properties are completely appropriate to produce locally, allowing the fab-
rication of all 2D material devices with dissimilar regions of various properties [128,129].
4. Classification of 2D materials
In order to accomplish the reliable synthesis, detailed understanding of the properties and induc-
tion in a multitude of applications, it is essential to understand the 2D materials structure composed
of single atom thick or single-polyhedral-thick layer. Therefore, 2D materials are categorized in three
classes.
4.1. Layered van der Waals solids
These types of materials are the front-runner and the most common material to exfoliate mono and
few layered nanosheets. These materials exhibit strong in-plane covalent or ionic bonding and weak
out of the plane van der Waal or hydrogen bonding. The weak nature of van der Waal bonding (40–
70 meV) and surface tension (60–90 mJ/m2) in the range of common solvents used for graphite
exfoliation facilitate the exfoliation of bulk parent crystals into nanosheets either by micromechanical
exfoliation or liquid exfoliation [130,131]. Once exfoliated these nanosheets possess a high surface
area and aspect ratio. These exfoliated nanosheets are usually few lm in lateral size and less than
1 nm in thickness. Transition metal dichalcogenides (TMDs) (MX2 (X–M–X layer) where M = Mo, Bi,
Ta, V, Ti, Nb, W, Hf, Zr and X = S, Se Te) are a well-studied system for layering van der Waals solids,
especially MoS2, MoSe2 and WS2. Currently over 40 different TMDs have been reported in layered form
[132]. Exotic properties of single and few layer derivatives in term of direct and indirect band gap,
Dirac point, electrochemical and mechanical behavior have emerged them as 21st century material
having potential in numerous applications such as semiconductor [133], hydrogen production
[134,135], thermo-electric devices [136] etc. In TMDs, transition metal occupies octahedral coordi-
nates (for d0, d3, and some d1 metals) and trigonal prismatic coordinates (for d1 and d2 metals) in
IT and 2H crystal structure, respectively. These coordinates share edges with nearest neighbors within
each layer and form hexagonal honeycomb like structure [131,132]. h-BN [137], SiC [138], vanadium
oxide [139] and Sb2Te3 [140] are some other member of this class.
4.2. Layered ionic solids
Layered ionic compounds constitute another important class of layered 2D materials that have
been gaining popularity. These types of solids consist of a charged polyhedral layer sandwiched
between hydroxide or halide layers by electrostatic forces. Single and few layered materials can be
easily exfoliated by ion intercalation or ion exchange liquid exfoliation method. Adsorption of bulkier
foreign molecules and exchange of parent ions with heavier ions increases the spacing between the
basal planes and weakens the basal plane bonding. Exfoliated europium hydroxide is a classic example
of layered ionic solids [141]. Perovskite type oxides such as La0.90Eu0.05Nb2O7 [142], K1.5Eu0.5Ta3O10
[143], KLnNb2O7, K2Ln2Ti3O10, and RbLnTa2O7 (Ln: Lanthanide Ion) [144], KCa2Nb3O10 [145,146], metal
hydroxides such as Eu(OH)2.5(DS)0.5 [141], Co2/3Fe1/3(OH)1/3+2 [147] are some examples of layered
materials exfoliated from the ion-exchange method. The measured thickness of monolayers is usually
higher than the crystallographic thickness due to the adsorption of solvent and bulkier exchanged
ions. These materials are discussed in detail in Section 8.4.
4.3. Surface assisted nonlayered solids
This class of atomically thin layered material is artificially synthesized on a substrate via chemical
vapor deposition and epitaxial growth. Silicene, an analogue of graphene, is a perfect example of sur-
face assisted nonlayered solids. Low buckled hexagonal structure of Si atoms has been deposited on
Ag(1 1 1) [150], Ir(1 1 1) [151] and a thin film of ZrB2 on silicon wafer [152]. Unlike graphene, instability
of silicene at the ambient condition has limited its potential in electronic and optoelectronic applica-
tions. Silicene has been discussed in detail in Section 8.3. Al2O3/SiO2 [153], Cu2N/Cu(1 0 0) [154], MgO/
Mo(0 0 1) [155], TiO2 [156]; and Ge/Ag(1 0 0) and Ag(1 1 1) [157–161] nanosheets are grown for appli-
cation in energy storage, field effect transistor (FET), controlling the charge density of nanoparticles. In
Fig. 6, we show the glimpse of atomic arrangements in different classes of 2D materials (MoS2,
La0.90Eu0.05Nb2O7, silicene and MnO2).
5. Synthesis methods for 2D materials
5.1. Micromechanical exfoliation using scotch tape
Atomically and few layers thick sheets of 2D layered inorganic materials can be obtained by
micromechanical exfoliation. This technique is similar to the method used by Grim and his coworkers
to separate single layer graphene from highly oriented pyrolytic graphite (HOPG) [162]. Commercially
available inorganic layered material is rubbed/peeled off against scotch tape on photoresist surface.
Fig. 6. Atomic arrangement in different classes of layered 2D materials. MoS2 and MnO2 from Ref. [148], layered ionic solids
from Ref. [149] and silicene from Ref. [38]. Reprinted by permission of the American Association for the Advancement of Science
and ACS Publishers.
This process leaves a variety of flakes including monolayers on the photoresist surface due to the
cleavage of weak van der Waal forces between two layers. These monolayers are washed with acetone
and transferred on oxidized silicon wafer. This method has been employed to obtain monolayers of
WS2 [163], MoS2 [164,165], h-BH [165,166], NbSe2 [165], Bi2Sr2CaCu2Ox [165] from the bulk.
However, this process is relatively simple, fast and cost effective but it has certain disadvantages.
As we know monolayers are second building block of layered materials, therefore, to understand
the fundamental/intrinsic properties of materials, separation of monolayers from thicker flakes is
necessary. The monolayer yield of this process is extremely low; hence, this method is only suitable
for laboratory scale studies and cannot be utilized for large-scale production for high end technologi-
cal application. On the other hand, since this process does not utilize any chemicals and only rely on
the shear force applied during the peeling process, structural integrity, and high crystallinity are main-
tained. After the cleavage of inter-planer van der Waal bonds, optical microscopy (phase contrast due
to single and few layers) and AFM (thickness measurement in tapping mode) are employed at their
best to screen the monolayers from thicker structures. Characterization of single and few layer sheets
is discussed in detail in Section 6. Single and few layers of exfoliated 2D layers are stable at ambient
conditions for days to months similar to single graphene layer as evident from the time dependent
high resolution transmission electron microscopy (HRTEM) and scanning tunneling microscopy
(STM) [165,167].
5.2. Liquid exfoliation
As discussed in the previous section, mechanical exfoliation of 2D layered materials is a semi-

quantitative low yield method, therefore it was necessary to develop facile methods for high quality
and large quantity of single and few layer of 2D materials. As an alternative to mechanical exfoliation,
liquid exfoliation is a reliable method to produce single and few layers 2D sheets at bulk scale. This
method has been extensively used to obtain mono and few layers nanosheets of MoS2, WS2, BN,
NbSe2, NiTe2, MoTe2, MoSe2, TaSe2, Bi2Te3 and so on [130,133,168,169]. The liquid exfoliation method
has four different forms: (i) oxidation, (ii) intercalation (iii) ion exchange and (iv) ultrasonic cleavage
[148].
Oxidative liquid exfoliation is an established technique for the synthesis of graphene oxide.
Graphite flakes are treated with sulfuric acid or nitric acid or mixture of sulfuric and nitric acid;
and potassium chlorate/potassium permanganate to passivate the surface of individual graphite layers
with the addition of OH or epoxide functional groups and their subsequent dispersion in polar solvent
and sonication results in the exfoliation of graphene oxide. This method is popularly known as a
Hummers method (sulfuric acid) or modified Hummers method (mixture of acids) [170,171]. It is to
be noted that extreme care should be taken while selecting the suitable oxidizer and solvent for dif-
ferent layered material. Layered materials having low reduction potential are best suited for this
oxidative liquid exfoliation.
Weak out-of-plane bonding in the layered materials and high surface area results in the opening for
molecules to be adsorbed on the basal planes and from inclusion complex. The Intercalation of organic
or ionic species causes the weakening of interlayer adhesion due to the increase in the interlayer spac-
ing and energy barrier required for the exfoliation. Similar to graphite, this method has been mainly
applied for TMDs. On the other hand, ionic species intercalate and exchange ions present on the basal
planes by charge transfer and weakening of interlayer adhesion. Ion exchange liquid exfoliation has
been widely used to exfoliate oxide nanosheets for optoelectronic applications [172]. In the ion
exchange exfoliation process, layered europium (Eu(OH)2.5Cl0.50.9H2O) first react with dodecyl sulfate
(DS) by replacing Cl ions in ion exchange process followed by ultrasonication or shear mixing to
separate the positively charged sheets [141]. Similar to europium hydroxide, TiO2 layered crystals
are tends to be negatively charged and their charge neutrality is maintained by Cs+ ions. Therefore,
negatively charged oxides are treated with bulkier cations such as tetrabutylammonium. This method
is widely known as proton exchange and has used in the exfoliation of perovskite type oxides men-
tioned in Section 8.4.
Ultrasonic cleavage of weak out-of-plane bonding is another liquid exfoliation method to obtain
mono and few layer nanosheets. Bulk layered material is dispersed in suitable solvent and
ultrasonicated for 1–3 h. These high energy ultrasonic waves create cavitation bubbles in the solvent
[148]. Sudden burst of cavitation bubbles generates high energy via release of pressure followed by an
exfoliation of layers in the solvent. The resultant dispersion is centrifuged to separate large thickness
crystals. Ultrasonication time and centrifugation rate are some of the critical parameters which dictate
the quality of the resultant solution. Mono and few layers nanosheets remain suspended in the super-
natant solution. Selection of optimum solvent is key to tap the full potential of this technique. Detailed
studies have been carried out for [130] more than 25 solvent on the exfoliation nature of a wide range
of 2D material based on the yield, crystallinity, thickness and size of the resultant layers. Solvents hav-
ing surface tension 35–40 mJ/m2 maximize the exfoliation rate examined using UV–Vis spectroscopy.
Use of solvent having surface tension similar to surface energy of layered 2D material not only mini-
mize the energetic cost of exfoliation but also prevents the restacking of nanosheets [130,148,173].
Earlier comprehensive study [130] has acted as a catalyst for the synthesis of 2D layered materials
with yield of up to 30 mg/mL [148,173–175]. NMP, DMF, DMSO, IPA, cyclohexyl-pyrrolidinone, N-
dodecyl-pyrrolidone, NVP are used as common solvents for ultrasonic exfoliation of h-BN, MoS2,
WS2, MoTe2, VS2 [130,169,176–180]. Aqueous solution of surfactant or polymer has also been utilized
to exfoliate nanosheets that are electrostatically or sterically stabilized. Nanosheets obtained from
ultrasonication are highly crystalline and micrometer in size as confirmed from HRTEM. However, it
is also reported that, the in-plane cleavage of layered materials in gadolinium hydroxide with an inter-
layer of Cl anion results in flakes of 100 nm size [181]. Schematic representation of the various liq-
uid exfoliation processes is presented in Fig. 7.
Density gradient ultracentrifugation (DDU) of 2D material containing solution further allows the
separation of single layers from few layers. This technique was first successfully applied to separate
single layer graphene oxide using sodium cholate as intercalating agent (surfactant) from the solution
[182]. Buoyant density difference of mono and few layer nanosheets separate single layer, few layers
and bulk crystals. Despite the large scale production ability of this method, mechanical exfoliation
remains the preferred choice for layered 2D materials due to the less destructive nature as well as
mono layers of size up to 10 lm have been peeled off on a variety of substrates [131,8].
Fig. 7. Schematic representation of variation in liquid exfoliation process: (a) intercalation, (b) ion exchange and (c) ultrasonic
exfoliation. Reprinted from Ref. [148] with permission of the American Association for the Advancement of Science Publisher.
5.3. Chemical vapor deposition (CVD)
The CVD technique has enabled the synthesis of large area and uniform thickness 2D layer of metal
and insulating surfaces for the large-scale device fabrication including electronic and flexible
optoelectronic devices. Recently MoS2 nanosheets have been grown on insulating oxidized silicon sub-
strate using two step bottom-up approaches [183]. First, a Mo thin layer was deposited on oxidized
silicon substrate by e-beam evaporation. Second, elemental sulfur was heated just above the melting
point to generate vapor further reacting with the Mo thin film at 750 °C and form 2D MoS2. However,
this method does not provide atom thick layer of MoS2 (1–3 layers). Moreover, 0.72 nm thick MoS2
single layers has been synthesized in one step bottom-up approach using MoO3 and elemental S at
650 °C [184]. Before the decomposition of precursor, SiO2/Si substrate was first coated with GO to
serve as a growth template for MoS2 layer. In another attempt to obtain large size MoS2 sheet, SiO2/
Si substrate was dip-coated with ammonium thiomolybdate ((NH4)2MoS4) dissolved in DMF and
annealed at 500 °C (Fig. 8) [185]. During the second step, annealed substrate was heated to 1000 °C
and allow to react with sulfur vapor. During the thermolysis process, (NH4)2MoS4 forms MoO3 which
later converted into MoS2 after reacting with S vapor at temperature above 800 °C. Another research
group [186] has studied the growth and grain boundary structure of CVD grown MoS2 layer on SiO2/Si
substrate. They have shown the evidence of grain coalescence during growth of MoS2 grains results in
the formation of an array of dislocation of 5–7-fold rings. Additionally, the growth of one grain above
another grain without any chemical bonding have also been observed.
Besides MoS2, h-BN has been extensively prepared and studied using CVD on transaction metal sur-
faces such as Pt, Ni, Ru, Pd, Rh, etc. for well-ordered layer structure BN by thermal decomposition of B-
trichloroborazine (ClBNH)3 or borazine (BN)3H6 [187–191]. Extreme conditions, including high tem-
perature (>700 °C) and ultra-high vacuum are required for this CVD process. It is worth mentioning
here that a lattice mismatch between the metal surface and BN result in the formation of two different
superstructures, i.e. types A and B [187]. In case of minor lattice mismatch, type A structure develops
during the CVD process, whereas for large mismatch such as in the case of Pt(1 1 1) (mismatch 11%)
both types A and B structure form as observed from low energy electron diffraction (LEED) pattern
(Fig. 9a). For type A structure, B atoms prefer to stay at hcp or fcc sites and N atoms at the top of
the substrate atoms (Fig. 9b). While in type B structure, B and N atoms are at on top of the metal sur-
face atoms and on the bridge sites (Fig. 9c).
5.4. Van der Waal epitaxial growth on substrate
Van der Waal epitaxial is an another form of CVD method. In contrast to CVD where substrate sur-
face acts as a catalyst, substrate often acts as a seed crystal. This method has been employed to fab-
ricate atom thick, large aspect ratio several 2D material such as hexagonal Si [150], h-BN [187], GaSe
[192,193], MoS2 [194], etc.
In-situ deposition of Si on Ag(0 0 1) by direct current heating of Si wafer under ultrahigh vacuum
condition develop two distinct superstructures in Si stripe examined using XFRD, STM and LEED
Fig. 8. Schematic representation of dip and anneal technique for large area MoS2 nanosheet synthesis. Insulator substrate was
first dip coated with Mo precursor followed by annealing under optimized conditions. Resultant product is uniform large
surface area MoS2 nanosheet. Reprinted from Ref. [185] with permission of ACS Publisher.
Fig. 9. (a) LEED pattern of Pt(1 1 1) surface and h-BN/Pt(1 1 1) surface showing both types A and B structure. Atomic model of (b)
type A and (c) type B structure in h-BN layer. Reprinted from Ref. [187] with permission of ACS Publisher.
[195]. A p(3 3) superstructure was observed during the first stage growth of Si nanostructure up to
single monolayer followed by a complex superstructure denoted as p(7 4). Both the structures were
oriented along the [110] or [1 1 0] direction of Ag substrate. The unit cell of p(3 3) consists of two
tilted dimers arranged in a rectangular fashion to make one Si tetramer. Fig. 10a and b shows the filled
state STM image and atomic model reconstruction of p(3 3) superstructure on Ag(0 0 1). In the unit
cell, side distances of the tetramer measured by SXRD are 0.234 nm and 0.40 nm whereas the height
distance between Si atoms are 0.13 nm. Further growth of monolayer develops 2 nm wide stripes hav-
ing p(7 4) superstructure on p(3 3) structure containing defects and no long-range ordering were
observed (Fig. 10c). The width of the stripe is equivalent to 7aAg and two joined hexagons equivalent to
4aAg. Detailed atomic reconstruction model of p(7 4) superstructure is shown in Fig. 10d. It is worth
to mention here that these self-organized Si structure produce minor distortion in the Ag substrate. On
Ag(1 1 0) substrate, 1.6 nm width and 0.2 nm thick Si nanoribbons with honeycomb structure were
synthesized by direct current deposition [196,197]. On the other hand, Ge tetramers structure
p p
p(2 2 4 2)R45° on Ag(0 0 1) produces a strong distortion in Ag substrate due to high solubility
in Ag [198]. Germanium monolayer have also been tried to synthesize on Ag(1 1 0) and Ag(1 1 1) sub-
strates. On Ag(1 1 0) substrate, 0.5 Ge monolayer coverage was obtained which has c(4 2)
Fig. 10. Filled state STM images of Si nanostructure developed on Ag(0 0 1) substrate showing unit lattice (a) p(3 3), (b)
p(7 4) and (b and d) their corresponding atomic model reconstruction. Reprinted from Ref. [195] with permission of Elsevier
Publisher.
superstructure examined from LEED [199,200]. This c(4 2) superstructure consists of two tetramers
per unit cell [199,200]. However, for Ag(1 1 1) substrate, different superstructures have been observed.
p p p
Initial 1/3 Ge monolayers show a ( 3 3)R30° that convert into c( 3 7) superstructure on 1
p
monolayer Ge coverage [199,201]. This c( 3 7) consists of four Ge tetramers per unit cell.
Further changing the substrate to Ag(1 1 1) (Fig. 11a), precise control of substrate temperature
(250 °C) and Si flux resulted in the synthesis of single monolayer of silicene where Si atoms are
arranged in a honeycomb lattice examined by STM (Fig. 11b) [150]. A height difference of 0.02 nm
in line profile of the STM image gives the evidence of Si atoms being present in two different sub-lat-
tices suggesting the possible formation of sp2–sp3 hybridization. Peak-to-peak and valley-to-valley
analysis measures the Si–Si atom distance to be 0.19 ± 0.01 nm which is significantly lower than
the bulk Si (0.235 nm). LEED analysis characterized the silicene monolayer consists of
p p
(2 3 2 3)R30° superstructure having long range periodicity (Fig. 11c) [150]. This discrepancy in
the Si–Si distance from the silicene structure has been explained by the misinterpretation of pure
Ag(1 1 1) surface [202].
p p
Recently, researchers have also fabricated buckled silicene having ( 3 3) super lattice struc-
p p
ture consider with ( 7 7) superstructure on Ir(1 1 1) substrate obtained from LEED [151]. These
findings were further supported by DFT based first principles calculations performed using the
Vienna ab initio simulation package (VASP). The projector augmented wave (PAW) potentials and
generalized gradient approximation were utilized in the first principle calculation. Similar to the
Ag(1 1 1) substrate silicene, height difference has been observed between Si adatom layers.
However, the Si–Si nearest-neighbor distance is measured to be 0.72 nm. The relaxed lowest energy
Fig. 11. Filled state STM image of (a) Ag(1 1 1) substrate and (b) hexagonal silicene. (c) Orientation relationship of Si with
Ag(1 1 1) surface showing unit cell. Reprinted from Ref. [150] with permission of AIP Publishing LLC.
configuration from DFT reveal that a single unit cell is made of six Si atoms present in different chemi-
cal environments. One Si atom is directly on top of an iridium atom; two atoms at the hcp hollow and
fcc hollow sites of the Ir(1 1 1) lattice; and the rest are at the bridge sites which result in the buckling in
the silicene monolayer.
Besides the substrate orientation, deposition temperature also causes the change in the orientation
p p p p p p
of Si nanostructure. Four different orientations i.e. (4 4), ( 13 13), (2 3 2 3) and ( 7 7)
have been reported for Si nanostructures on Ag(1 1 1) substrate at various temperature [203–206].
Moreover, epitaxial growth of MoS2 has been reported on CVD grown graphene on Cu foil which
act as a template where dangling bonds and intrinsic weak van der Waal forces assist in the growth
process [194]. Use of CVD grown graphene–Cu template also able to lower the deposition temperature
to 400 °C.
As discussed in the above examples, van der Waal epitaxial growth of thin layers allow the fab-
rication of large sheets of novel 2D material which is not possible through liquid exfoliation and
hydrothermal methods. However, substrate chemistry and orientation are critical to obtain the
desired structure and properties. Harsh temperature, controlled atmosphere, and high cost limit the
wide use of van der Waal epitaxy in future commercial application.
5.5. Hydrothermal synthesis
Crystallization of substance at high temperature and at high vapor pressure from aqueous or
organic solution is primarily defined as hydrothermal method. It is particularly suitable for precursor
having best solubility and stability of growth phase at high temperature and high pressure. Materials
having high vapor pressure near the melting point can also be synthesized by hydrothermal method.
This method has been employed for the synthesis of layered 2D materials. Chemical reaction between
ammonium molybdate [(NH4)6Mo7O244H2O] and sulfur and/or selenium in hydrazine monohydrate
solution at 150–180 °C for 48 h results in the synthesis of single monolayer MoS2 and MoSe2 [207]. The
presence of single layer was confirmed by the absence of (0 0 2) diffraction peak in the XRD spectrum.
It is important to mention that no restacking tendencies were observed in both monolayers samples
without the use of surfactant. MoS2 flakes of 3–10 layers were reported in the literature on GO in a
one-step solvothermal reaction of (NH4)2MoS4 and hydrazine in DMF solution for hydrogen evolution
[134]. Inspired by the finding of single and few MoS2 layers, use of hydrothermal method has been
extended to obtain other 2D layered materials.
Recently the synthesis of groups IV and V transaction metal chalcogenides crystals from metal
chloride in oleylamine is reported [30]. CS2, elemental S and Se were used as the primary chalcogen
source. Poor crystallinity and irregular shaped crystal were observed in the case of elemental S due
to the formation of highly reactive radicals, whereas the use of CS2 generate intermediate H2S which
further reacts with the metal precursor and form metal disulfides crystals of (0 0 1) layers of varying
lateral size (Fig. 12a and b). Growth of layered nanocrystal in (0 0 1) plane is attributed to the low
Fig. 12. (a) Chemical reaction for the synthesis of TiS2 layered nanocrystal. (B) HRTEM image of TiS2 nanocrystal from reaction
(a). (c) Schematic representation of growth model of ToS2 nanocrystal based on surface energy. (d) TEM image showing the
radical effect on crystal while reaction with AIBN at 300 °C. (e) Morphological change in TiS2 nanocrystal with time when react
with elemental S. (f) TEM images of TiSe2 nanocrystal change when react with elemental S and Se. Reprinted from Ref. [30] with
permission of ACS Publisher.
surface energy in (0 0 1) plane compared to the (1 0 0) and (0 1 0) plane (Fig. 12c). Contrary to S, use of
Se as chalcogen source gives better layered crystals due to its high stability compared to CSe2 [208].
This article also demonstrates the effect of radicals on TiS2 and TiSe2 nanocrystals with time. Reaction
of TiS2 crystal at 300 °C with S and AIBN degraded the crystal due to the radical generation of highly
reactive nature, whereas mild degradation was observed for TiSe2 crystal (Fig. 12d–f). On the other
hand, the reaction of radicals does not degrade the closed pack zinc blend structure compounds sug-
gesting that radicals react only on the edges and penetrate between the open spaces of two layers to
react with these layered crystals. Therefore, the selection of low reactive radical generating chalcogen
is needed to synthesize such layered nanocrystals.
Facile large scale production of nanosheets from the hydrothermal method also makes it an attrac-
tive choice for industrial incubation. Recently, h-BN of 4 nm thickness were prepared on the gram
scale from boric anhydride, Zn powder and N2H42HCl at 500 °C [209]. Similar results were obtained
from the reaction of boric acid and urea at 900 °C [210]. Besides TMDs, this method has also been
extensively utilized to prepare nanosheets of metal oxides and hydroxides. Hydrothermal reduction
of V2O5 in the presence of graphene oxide (GO) result in the formation of VO2 nanoribbons of thickness
10 nm, width 50–500 nm and length 10 lm on graphene oxide nanosheets for the cathode mate-
rial in lithium ion batteries [139]. Synthesis of Eu doped yttrium hydroxide nanosheets and nanotubes
have been reported via hydrothermal method using triethylamine as alkaline and complexing agent
[211]. HRTEM, XPS and STM characterization have revealed high crystallinity and composition control
on such crystal grown by a hydrothermal method. These synthesized 2D materials can be resuspended
in the desired solvent and deposited to prepare nanocomposites, nanodevices and future nanotechnol-
ogy applications.
6. Characterization methods
Examining the vibrational and molecular structure of 2D nanostructured materials is integrally

interesting due to their size. On the other hand, various approaches have been established to facilitate
their description and credentials. In this section, we will discuss the basic principles of selected
characterization techniques and their use for analyzing single- and multilayer-thick materials. In
addition, we will also highlight recently developed techniques, which have the potential to explain
structural and spectroscopic information about the layers.
6.1. Microscopy techniques for 2D materials
The optical properties of 2D materials are heavily affected by their physical structure, which can be
studied using various microscopy techniques. Mainly atomic force microscopy (AFM), scanning elec-
tron microscopy (SEM), ultrasonic force microscopy (UFM), and transmission electron microscopy
(TEM) is used for morphological and topographical analysis.
6.1.1. Atomic force microscopy

The AFM uses a sharp tip with a radius of nanometer magnitude, which is attached to a cantilever.
When the tip is brought close to the sample surface, in the case of 2D layers electrostatic forces act on
the tip, which makes the cantilever bend according to Hooke’s law. This force is detected by the deflec-
tion of a laser against the cantilever, into a photodiode detector. An electronic feedback detection sys-
tem repositions a piezo stage where the sample is held, which moves the sample up and down,
keeping the tip at a constant height above the surface. Many researchers have used AFM to measure
the thickness of 2D layers.
AFM is an influential technique to identify layer thickness (Fig. 13b and c) with 5% preciseness
[212–215]. However, inconsistencies originate from dissimilarities in the tip interactions with sub-
strate and the layered materials [216]. For example, a single layer thickness could be known by eval-
uating the height between the first two layers, instead of measuring the height between the substrate
and a first layer because the tip-layer interactions are constant in the former. To achieve the perfect
Fig. 13. (a) Optical micrograph of MoS2 layer [217] (b) AFM of MoS2 [217], (c) AFM of graphene [215], (d) optical micrograph of
graphene [215], (e) FQM image of graphene using PVP/fluorescein [215]. Scale bars are 10 lm. Reprinted by permission of ACS
Publishers.
height profile of a single layer and control these differences, it is essential to optimize the tip-surface
distance from any hysteretic pieces [216].
6.1.2. Ultrasonic force microscopy

UFM can also be used to measure the stiffness of materials (for example, mechanical coupling to
the substrate) on the nanometer scale [218,219]. For this technique, the sample is vibrated at small
vibrational amplitude (0.5–2 nm) and high frequency (2–10 MHz), greater than the AFM cantilever
resonance frequencies. The restoring force of the sample is then modified by the stiffness of the mate-
rial, and this can be used to detect below-surface features such as cavities, subsurface interfaces and
sample-substrate interfaces. UFM can be measured concurrently with AFM, detected on a separate
channel where ultrasonic vibration at the tip-sample junction is converted into an image by nonlinear
rectification. Many researchers have used UFM to detect nanometer scale resolution of stiffness of 2D
structures of few atomic monolayers of layers. An example UFM image of MoS2 is given in Fig. 13a
[217,220]. In this case color variation correspond to sample stiffness. This is used to detect below sur-
face defects, regions of suspension and measure mechanical coupling of 2D materials with the sub-
strate [217,220–222]. Others, used this technique to the show weak mechanical bonding between
the substrate and the layers for free standing sheets and strong mechanical bonding when a dielectric
capping layer is added [212,213,223].
The primary task in the mono-layer description is preparation and recognition. The simplest tech-
nique is mechanical exfoliation in which 2D nanosheets from bulk materials such as graphene
[11,37,224,225], and metal chalcogenides [226] are transferred to a suitable substrate. In the begin-
ning, optical microscopy was the dominant high-output technique for classifying single- and/or
few-layer material [224,226–228]. The most common substrates are dielectric-coated SiO2/Si sub-
strates which are very useful to observe and differentiate between single and few layers in nanoscale
(Fig. 13a, d and e). The dielectric covered wafer color depends on an interference influence, which are
reflected from the two surfaces. The layered materials (single- or few-) on the dielectric surface pro-
duce a color difference between the substrate and the layers [227,229]. In place of ideal color contrast,
the dielectric coating thickness should be less than 5 nm for the perfect measure. On the other hand,
refraction indices for several materials are unidentified, it is frequently essential to exfoliate onto a
various substrates having various dielectric thicknesses in order to obtain the ideal thickness.
Imaging mono layers on different substrates free from interference methods has also been discov-
ered. Some TMDs (MoS2, WS2) have direct band gaps when it is mono layers, enabling their uninter-
rupted visualization using fluorescence microscopy [219]. On the other hand, when single layers
changes to multiple layers, these TMD materials band gaps convert to indirect, thus their fluorescence
will be significantly decreased. Fluorescence Quenching Microscopy (FQM) can be used for an organic
fluorophore whose fluorescence is quenched with mono- or multi-layer sheets (Fig. 13e). Various layer
structured materials characteristic either low enough band gaps or the suitable band alignment to
reduce nearby fluorophores using a fluorescence resonance energy transfer mechanism (FRET).
Mono layers of any 2D materials can be identified on a substrate by observing the decrease in fluores-
cence intensity of a thin fluorophore layer that was spin-coated on the top [220,222,230].
6.1.3. Electron microscopy techniques

Diffraction limits the resolution of an optical microscope to around 1 lm. Electrons have a small de
Broglie wavelength, and therefore higher spatial resolution can be achieved. Frequently used micro-
scopy methods are SEM and TEM. A focused beam of electrons is produced thermoionically in a tung-
sten/LaB6/field ion gun cathode and raster scanned across the surface of the sample. Secondary
electrons are emitted from the sample due to inelastic scattering within a few nanometers to a couple
of micrometer from the surface [212]. Electrons are collected by a scintillator grid, which converts the
intensity into an image. The resolution of the SEM is normally <50 nm [223]. Unlike SEM, where sec-
ondary electrons are emitted from the sample surface, electrons in TEM are transmitted through the
entire sample; usually after the sample has been thinned to nm thickness. The electrons interact with
the atoms during transmission and deflection can be used to produce an image [213]. TEM has a
higher resolution compared to SEM as high voltage (200–300 kV) is used to generate electrons in
TEM which has a shorter wavelength and thus enhance the resolution, but requires samples to be
extremely thin (<200 nm) which is a disadvantage for many systems [223].
These techniques can provide comprehensive evidence on the crystalline nature, interlayer stack-
ing relationships, layer sizes, and elemental configuration (Fig. 14a and b) [107,212,214,226,231,232].
For graphene, selected area electron diffraction (SAED) may differentiate a monolayer or multilayers
when the (1 1 0) to (1 0 0) diffraction intensity ratio is smaller or larger than one. This aberration in
diffraction intensity could also be distinguished within the monolayer or multilayer of any 2D materi-
als when there is a variation in interlayer recording. Dark-field microscopy is the recent development
for identifying the layer numbers and stacking order of the layered material [233,234]. Scanning trans-
mission electron microscopy (STEM), coupled with electron energy loss spectroscopy (EELS) could be
very useful for imaging an individual or separate atoms in a single layer. In this technique, a sub-ang-
strom electron beam is formed across the material and it is scattered as soon as it strikes a particular
atom. A STEM image of oxygen and carbon substitutions in a boron nitride single layer has been shown
in Fig. 14c. In STEM, beam damage can be reduced by imaging at low accelerating voltages (<60 keV).
Another important probe based technique is Scanning Tunneling Microscopy (STM) which can be
used to evaluate the topographic and electronic structure of single layered materials. This technique
could control single atom at exact points in order to characterize the 2D layer materials that are
detached from the substrate (Fig. 14d) [235]. For Examples, STM studies of MoS2 nanoislands [236]
and BN [237], as well as characterization of the unusual cyclotron quantization in graphene
[238,239]. At present concentration has been shifted to the adsorbates and defect studies, containing
metal atoms on graphene [240,241] and hexagonal BN [242,243] and molecules on MoS2 [244].
Epitaxially grown layers are the most commonly studied samples in STM because of the alignment
challenge in a specific part of the substrate with the distant STM tip. Near-field tip-enhanced
Fig. 14. (a and b) Low and high resolution TEM image of a 2D WS2 crystal [232], (c) Annular dark field-STEM image of a single
BN layer and part of DFT simulation observed substitutional impurities overlaid on the corresponding part of experimental
image. (yellow, green, blue, and red colors are corresponds to C, N, O, and B, respectively) [234], (d) STM image of a Cu2N island
with adsorbed Co atoms on Cu site (top center) and N site (bottom left) (0.1 V, 0.25 nA) [235]. Reprinted by permission of ACS
Publishers, Nature Publishing Group, and AIP Publishing LLC.
Raman spectroscopy (TERS) is nothing but silver or gold coated tip in AFM or STM which can improve
the local Raman spectra. This technique has established to be a great combined image and spectro-
scopic technique, for example, it is very useful to find defects and grain boundaries of TMD layers
[245].
6.2. Raman spectroscopy
When a sample is irradiated, despite of being absorbed by the sample and then reemitted, a small
proportion of the incoming light is scattered at a wavelength that is shifted from the original laser
wavelength. Raman Spectroscopy is based on an inelastic scattering of monochromatic light. There are
two kinds of inelastic scattering. Stokes (output energy is smaller than input energy) and anti-stokes
scattering (output energy larger than input energy). The difference between the output and input light
provides the information of vibrational modes, which are materials fingerprints.
The vibrational modes of MoS2 are shown in Fig. 15a. Among them, the two strongest Raman peaks
are E12g and A1g modes. E1g mode cannot be seen due to the selection rules [246] and E22g mode is also
unable to be observed because of the limited rejection of Rayleigh scattered radiation [247]. E1u mode
is not Raman active.
Raman spectra of MoS2 are thickness dependent [217]. As thickness increases from single-layer to
bulk, E12g vibration makes red shifts and A1g vibration makes blue shifts (Fig. 15b and c). The E12g peak is at
382 cm1 and the A1g peak is at 407 cm1 for bulk MoS2. The E12g peak blue shifts to 385 cm1 and A1g
peak red shits to 403 cm1 in single-layer MoS2. Therefore, the Raman peak frequencies of E12g and A1g
peaks can be used to determine the thickness of MoS2.
The Raman shift of MoS2 is the result of several effects. One of the reasons of the Raman peak shift
of MoS2 is the thermal effect of the laser [248]. Increasing the laser power will soften the bond, so the
Raman spectra will shift to the red side. Different soften rate cause the shift of E12g and A1g to different
direction. Another reason is interlayer van der Waals force, which could suppress atom vibration more as
thickness is increased [249].
6.3. Photoluminescence (PL) spectroscopy
PL is a photon emission process due to the recombination of an optically created electron hole pair.
For PL to occur in a semiconductor the absorption of a laser photon must stimulate an electron from
the valence band to the conduction band [250]. For electron promotion to occur the laser photon
energy must be the same or higher than the material band-gap. The radiative recombination of the
Fig. 15. (a) Vibrational modes of MoS2 (Z direction is out of plane), (b) thickness dependent MoS2 Raman spectra, and (c)
frequency difference between E12g and A1g mode. Reprinted from Ref. [217] with permission of ACS Publishers.
electron–hole pair may be preceded by a non-radiative relaxation mechanism, which leads to the
emission of phonons. Competition between the non-radiative and radiative processes is important
for most of the 2D nanostructured materials. Photo-excited electrons (holes) relax to the bottom of
the conduction (valence) band by emitting phonons [251]. Optical recombination of electron–hole
pairs occurs at the energies close to the edge of the band-gap [252]. If these band edges occur at
the same position of the Brillouin zone in momentum space (ie. have the same wave vector) emission
of a photon occurs with conservation of energy and momentum without further need for additional
processes such as emission of phonons. If they occur at different positions (ie. have different wave vec-
tors), then emission of a particle becomes a second order process and requires additional emission of
phonon in order to conserve momentum [253]. This is therefore a slower process and produces a lower
emission rate of photons. The first order process is characteristic to direct band-gap semiconductors
and is found in the case of most of TMD layers.
In an atom, electrons assemble in discrete energy levels and therefore produce a discrete flores-
cence emission spectrum with line widths determined by the uncertainty principle [254]. In semicon-
ductors the electrons and holes relax into the bottom of the valence and conduction band respectively,
forming a thermal distribution before recombining [250]. The line width of emission is related to this
thermal distribution KBT, where T is temperature and KB is the Boltzmann constant, along with the
density of states, carrier density and inhomogeneity of the crystal. If confinement becomes great
enough, quantum effects can occur. In the case of quantum wells and 2D materials such as MoS2,
the electron is unrestricted in movement in two directions, and confined in the third axis. This modi-
fies the density of states to a step like structure with each step corresponding to a confined energy
state [251]. On the other hand, localized strain on the atoms in a crystal lattice effect their relative
positions leading to a disordered band-edge. Radiative recombination of electron–hole pairs will
therefore have a slightly different energy at different positions in the crystal. There is an evidence that
non-radiative processes are dominant in the recombination of electron–hole pair in 2D materials. It
has been found that competition between radiative and non-radiative processes affect the behavior
of PL when varying temperature and incident power. There is an evidence to support previous results
showing a low quantum efficiency in 2D layers [21], finding that PL emission does not saturate at high
pumping power. Time resolved PL is also used to measure the temporal characteristics of light emis-
sion as a result of sample excitation with a pulsed laser. Typically, the PL decays in the nanosecond
range in structures where the electron–hole pairs are tightly bound [255]. Instead of continuous beam
of photons, 2D layers can be excited by very short laser pulses. The PL spectrum is then recorded as a
function of time from the arrival of the excitation pulse. Resolution of the detector plays an important
role in these experiments.
6.4. X-ray diffraction
X-ray diffraction (XRD) is a non-destructive analytical characterization method to determine the

crystal phase and structure. An X-ray diffractometer generates an X-ray beam striking a material as
a function of incident and scattered angle, polarization, and wavelength or energy. Both the unit cell
size and geometry are resolved from the angular positions of the X-ray diffraction peaks.
Wide angle XRD and small-angle X-ray scattering (SAXS) are highly used to collect the information
about the material structure and component, thickness of the sheet, and the placement of stacked
nanosheets. Inter-layer stacking peaks occur only at low angles which can be measured by SAXS
[231]. By pretending this pattern, sheet thickness, the stacking alignment, and distance between
two layers or sheets can be measured. For example, wet colloidal and dried aggregates of layers always
show different XRD peaks: only layer registry may be concerned for wet colloidal aggregates, however
the inner level lattice planes are retained, proposing detached nanosheets (Fig. 16) [256,257]. On the
other hand, for dried nanosheets, low-angle pattern shows a well-organized nanosheets arrangement
along the stacking axis, and similarly, the basal reflections disappears in the pattern shows random
alignments for the group of nanosheets [257]. The layer orientation on substrates helps the thin axis
alignment. Specific peak broadening under the layer orientation is the indication of the thin axis [258].
For additional information, the XRD pattern of nanosheets could be demonstrated by the Lorentz
polarization factor, the structural influence, the temperature influence and the Laue interference
Fig. 16. XRD patterns of nanosheets (a) bulk niobate, (b) wet colloidal aggregates of nanosheets as solid line: and calculated for
a single layer as broken line, and (c) dried aggregates of nanosheets. Reprinted from Ref. [256] with permission of Elsevier
Publishers.
function [212] [256]. Structural parameters for monolayer and multilayers could be computed assum-
ing the unit cell structure, atomic positions, and orientation to a substrate [212]. This modeling results
could help to find the nanosheets important units such as the spacing between the nanosheets, and if
the nanosheets are rearranged. Inner layer XRD information could be very useful to detect hkl reflec-
tions of the nanosheets 2D unit cell [212,214]. This hkl reflection measurement is a valuable technique
to detect absent peaks from well-ordered nanosheets on a substrate. By modifications of these data
unit cell parameters could be extracted and compared to bulk nanosheets. For example, XRD
investigation of Germanane (GeH) showed that it could be fitted to a 2H unit cell (2 GeH layers per
hexagonal unit cell spacing) with a = 3.380 Å and c = 11.04 Å (5.5 Å per layer). In the a-direction, the
hydrogen-terminated germanane is slightly contracted compared to the bulk unit cell parameters of
a = 3.987, c = 30.0582, (6 layer stacking, c/6 = 5.097 Å) but expanded in the c-direction due to the
replacement of Ca2+ with 2 Ge–H bonds between each layer [259].
The reflections from the basal plane will be absent in the case of single mono layer, whereas a peak
from the basal plane will appear in the XRD pattern for stacked nanosheets. The intensity of the reflec-
tion depends on the number of sheets stacked. A classic example of this is MoS2 [207]. (1 0 0) reflection
appears in the XRD pattern when single layer MoS2 is present with no (1 1 0) and (0 0 2) reflections. In
case of loose MoS2 agglomerates, (1 1 0) reflection also appears due to having no sign of (0 0 2) reflec-
tion. Whereas few layers stacked MoS2 shows all the three (1 0 0), (1 1 0) and (0 0 2) reflections due to
the appropriate orientation in between MoS2 nanosheets. Therefore, information regarding single and
few layer nanosheets can be easily obtained using XRD.
6.5. Characterization possibilities
The progress and execution of novel characterization methods which can non-destructively probe
and quickly investigate the structural and physicochemical properties of 2D layer materials is essen-
tial to improve the field. Most of the 2D layers are used for electronic application, it is important to
measure the electronic properties and it is mostly controlled by minority defects. Aberration corrected
STEM and STM is most powerful and incredibly valuable techniques which can easily identify minor
defects, edge states and other species present in the material. The development of imaging techniques
with spectroscopic combination such as Tip-Enhanced Raman Spectroscopy (TERS) can considerably
assist in identifying and characterizing the single layers and also it can minimize the substrate signals.
7. Nanomechanics of 2D layers
This section discussed the potential by using 2D materials to produce new nanomechanical, or
nanoelectromechanical systems (NEMS), which are nanoscale objects that can flex, move, rotate, or
vibrate. NEMS is useful for electrical signal processing as nanoscale switches, filters, and oscillators,
and as small scale manipulators of light or fluid flow [260–262]. Due to their small size, NEMS respond
very strongly to changes in their environment, making them useful in understanding the nature of the
forces [263], and mechanics [264,265] on very small length, energy, and time scales. They also have
practical applications as tiny ultra-sensitive sensors for measuring acceleration, strain, gas pressure,
electrical charge, and the presence of molecules.
7.1. Mechanical properties of 2D materials
The most fundamental mechanical properties of engineering materials lie in the linear response to
strain under stress, also known as Hooke’s law, which can be considered a mechanical equivalent to
Ohm’s law. If we apply a uniaxial compressive or tensile stress to the material, the relation can be
expressed as:
r ¼ Ee ð1Þ
where r stands for the stress, while e the strain. Materials usually differ from each other in E, known
as the modulus of elasticity or Young’s modulus [266]. Eq. (1) is a general Hook’s law and can be
applied to bulk as well as 2D nanosheets. The current form of equation r ¼ Ee is widely used to repre-
sent the stress–strain relationship of randomly oriented polycrystalline materials. However, if stress
and strain known for specific direction; elastic modulus can be determined for specific direction using
this equation. Therefore, the concept of plane stress and plane strain originates. Thus, transformation
stress and torque can be calculated. This can be further explained from the classic example of von
Mises criteria for yield locus are critical resolved shear stress for single crystal. Therefore, Eq. (1) also
holds true for 2D nanosheets and widely used to measure the in-plane elastic modulus of 2D mono-
layer [124]. The ratio of the strains (the lateral strain to the axial strain) in two different directions
defines a quantity known as Poisson’s ratio ‘m’. Some materials like the cork of a wine bottle have
m 0 while others like rubber have m 0.5. There is also exists a class of exotic materials with m < 0
[267]. Materials having a negative Poisson’s ratio are called auxetic materials. Materials having posi-
tive Poisson’s ratio become thinner in perpendicular direction to the applied force where as auxetic
materials become thicker in the perpendicular direction to the applied force. A few typical examples
of auxetic materials are vacancy defect introduced graphene [268], silicone rubber ‘‘Sil AD Spezial’’
(SADS) [269], special foams [270], carbon nanotubes sheets [271], molecular networks [272].
When applying shear loading to the material instead, we can write a similar equation:
s ¼ Gc ð2Þ
where s and c are the shear stress and strain, respectively, G is called the sharing modulus of elasticity
or modulus of rigidity of the materials. However, G is related to E and m as in an isotropic material:
E
G¼ ð3Þ
2ð1 þ mÞ
Accordingly, there are only two independent elastic constants. In practice, materials are usually
engineered into different types of structures, like 1D bars or frame structures. Planar or curved struc-
tures are a family of structures that have two dimensions much larger than the third one. Three family
members are included in the third type: panel, plates and shell. Panels are loaded only to in-plane
stress, while plates are subjected to out of plane loads as well. Shells are usually curved planar struc-
tures with very small thickness compared with their other dimensions, which only resist tensile and
compressive forces [273,274].
For instance, the Young’s modulus of graphene has been known for many years from measure-
ments of the mechanical properties of graphite. Experiments using AFM tips [275,276] and gas pres-
sure [277] to stretch, single and multilayer graphene membranes showed that the Young’s modulus of
graphene is E = 340 N/m. These experiments also showed that graphene is under an initial tension
before it is strained further by the AFM tip. These experiments measured the pretension to be
S0 = 0.07–0.74 N/m which is equivalent to a pre-strain of e = 105–104 [124,278]. By pushing on
the graphene with a diamond AFM tip [124], researchers were able to tear the graphene directly under
the AFM tip. They found that the breaking stress is 42 N/m corresponding with a strain of 0.25. These
measurement show that graphene is the strongest material on earth. On the other hand, the elastic
modulus of CVD grown single layer MoS2 and WS2 (170 N/M) was shown nearly half of that of gra-
phene. Theoretical prediction also shows the same elastic properties of MoS2 and WS2 [279].
7.2. Bulge test
It is a commonly used method to measure young’s modulus, Poisson’s ratio and residual stress of
thin films [280,281]. In the easy execution, the maximum deflection z, and a radius of curvature R is
measured by applying a pressure difference across a clamped circular film [282]. The pressure differ-
ence, Dp, applies a well-defined and uniform force across the layers of the thickness t, which is bal-
anced by the induced biaxial stress, r, in the 2D layers:
Dp:pR2 ¼ r 2pRt ð4Þ

DpR
r¼ ð5Þ
2t
In the bulge test, the 2D layer can be considered to be under uniform biaxial stress, we can get the
stress and strain relationship of the isotropic material as

E
r¼ e ð6Þ
1v
In the simplest case of an initially flat, unstressed layer, we can have the pressure displacement
relationship for an elastic material and gives the ‘‘bulge equation’’ for a circular layer [281]:
4So z 8Etz3
Dp ¼ þ 4 ð7Þ
a2 3a ð1 v Þ
For the geometry of a square layer, the equation is slightly modified to [281]
!
4z 4c2 Etz2
Dp ¼ c 1 So þ ð8Þ
W2 W 2 ð1 v Þ
where c1 = 3.393 and c2 = (0.8 + 0.062v)3 and for a rectangle this becomes
!
4z 16Etz2
Dp ¼ 2So þ ð9Þ
W2 3W 2 ð1 v Þ
where W is the length along the short end of the rectangle.

Using Eqs. (8) and (9) one can measure E and v by a bulge test performed on the same material in a
square and rectangular geometry. The plane-strain bulge test is another interesting technique for find-
ing the mechanical properties of 2D layers. This technique can be used to identify the layer stress and
strain from the pressure deflections [283]. Recently the fracture behavior of a single layer CVD-gra-
phene was measured using bulge test [284]. It was shown that the crack initiated and propagated
while increasing the pressure difference, Dp, at room temperature (20 °C) and the cracks are mainly
initiated at the edge when the pressure difference was between 1.5 and 2 kPa.
7.3. Nanoindentation
This method is a substitute to the bulge test for evaluating the elastic constant of free standing
structures. Commonly, a calibrated spring constant AFM tip is used to indent on a free standing struc-
ture and the deflection of the structure and tip is measured. This force–displacement curve helps to
deduce the local spring constant of the structure. Disregarding the bending rigidity, the tension could
be attained from the evaluated spring constant k, at the middle of the layers using S (k/2p)ln(R/r),
where R is the radius of the layers and r is the AFM tip radius [285]. A comprehensive theoretical
review of this method for indentation of 2D layers regime can be found elsewhere [286]. This well-
known method has been used by many researchers to measure the mechanical properties of few layer
graphene [287] and other 2D nanosheets [288,289]. For examples, nanoindentation studies were per-
formed the on single layer graphene to know how the mechanical properties are caused by defects
[290]. It was shown that defective graphene breaking strength is very less and elastic modulus is
maintained even at high density of sp3 type defects. It has been reported that the measurement of
the breaking strength and in-plane stiffness of monolayer and bilayer MoS2 sheets by nanoindentation
technique with an AFM tip on free standing MoS2 layers and calculated different mechanical proper-
ties such as Young’s modulus, pre-tension of the layer, and breaking strength [291].
7.4. Contact adhesion
Contact adhesion is an essential mechanical property of 2D materials and an interesting area of

study. Due to their atomic thickness and resulting incomparable flexibility, 2D layers can conform
to the contacting surfaces much better than bulk materials, thereby increasing the contact area and
adhesion significantly. The measured contact adhesion energy on graphene is comparable to that of
a liquid–solid interface [292,293]. Additionally, the adhesion energy of CVD grown graphene on Ni
and Cu substrates was evaluated to be 72.7 and 12.8 J m2, respectively [294]. For the same, density
functional theory also showed that the Ni–graphene interface shows more covalent bonding than a
Cu–graphene interface, hence the reason for the higher adhesion energy for Ni–graphene [294]. The
ultrastrong contact adhesion also plays an important role in the 2D materials and devices for them,
especially nanomechanical devices [295]. Take the NEMS switches as an example: the adhesion can
help the layer self-clamp over the trenches or cavities, which helps simplify the fabrication process,
on the other hand, a restoring force in the device, determines the required actuation electrical voltage,
and needs to overcome the contact adhesion between 2D layers and the underneath electrodes. This is
necessary to guarantee repeatable switching. Therefore, the ultrastrong contact adhesion can result in
an undesirably high actuation voltage for the device to repeatedly switch. How to make a reliable
NEMS switches with low actuation voltage requires the development of various approaches to
decrease the contact adhesion force. Similarly, MEMS switches also have been demonstrated recently
using MoS2 layers [296].
7.5. Blister test
Other than traditional methods to measure the contact adhesion in thin films/layers, including peel
test, pull test, and scratch test, the blister test turns out to be a widely used approach to probe the
adhesive property, especially in 2D layers, due to the ease of implementation and film preparation
[292,297–300]. The standard spherical blister test has the same configuration as that used in bulge
test, but when the pressure difference across the member is greater than a critical value the mem-
brane starts to delaminate from the substrate. Recently, researchers used a constant N (# of gas mole-
cules) spherical blister test to achieve stable delamination between graphene and SiO2 substrate and
the adhesion energy is calculated using a thermodynamic model to be 0.45 J m2 [292,295]. Another
research group applied constant N island blister test to getting stable and unstable delamination of
graphene from SiO2 substrate, and the adhesion energy measured is comparable, though slightly lower
0.1 J m2 [301].
7.6. Van der Waals force
Van der Waals free energy interaction between a single layer atomic membrane and a substrate can
be derived from the integration of pairwise potential energy from the atom–atom interaction based on
Hamaker summation method [302,303]. The Lennard-Jones potential for the pairwise interaction
between one atom on the membrane and a substrate atom is
C1 C2
W LJ ðrÞ ¼ þ ð10Þ
r6 r 12
where C1 and C2 are the constant for the attractive and repulsive interactions respectively, while r is
the distance between the atoms. By summing up the atom–atom potential for all the atoms in the
membrane, we have the monolayer-substrate interaction energy, namely
Z Z
W LJ ¼ Ag V s W LJ qs qg dV s dAg ð11Þ
Assuming the substrate has a flat surface while the monolayer membrane is flat as well, and they are
in parallel, then we can get the analytic form of the interaction potential between the membrane and
the substrate,
" 9 #
3
3 h0 1 h0
U v dw ¼ C0 ð12Þ
2 z 2 z
Where Uvdw is the monolayer-substrate interaction energy per unit area, z is the distance between the
monolayer and the substrate surface, h0 is the equilibrium separation, and C0 is the adhesion energy at
the equilibrium separation [304]. Recently it has been verified that van der Waals force is highly domi-
nant feature for the chemical reactivity of graphene on 2D heterostructure substrate [305]. In that a
significant enhancement has been achieved in the chemical stability by replacing the commonly used
SiO2 substrate with 2D layers such as MoS2, WS2 layers or h-BN nanosheets. Theoretical results also
show that chemical reactivity is high because of a strong van der Waals force between the graphene
layers and 2D heterostructure substrate [305].
8. 2D materials, their properties, and application
8.1. TMD layers
As we know that the bulk layered TMDs have strong intralayer covalent M-X bonds and weak inter-
layer van der Waals interactions, which may be cleaved to single- or few-layer TMDs. Whether these
materials are able to be exfoliated effortlessly depends on their surface energies. Surface energy is the
energy required to create new surfaces when the layered crystals are peeled; peeling would introduce
two new surfaces. The surface energy of MoS2 and WS2 (65–75 mJ m2 [107,306]) are similar to the
surface energy of graphene (65–120 mJ m2 [106,307]) making them potentially cleavable.
Theoretical results also reveal the stability of single-layer TMD (summarized in Fig. 17) [308].
Among them, chromium (Cr), molybdenum (Mo) and tungsten (W) based layered TMDs are semicon-
ductors. However, CrS2 and CrSe2 are not stable [309] and CrTe2 has a small band gap [310] with tri-
clinic structure [311]. Thus, only Mo and W dichalcogenides meet the requirements to form
semiconductors. Furthermore, Mo and W dichalcogenides have sizable band gaps around 1–2 eV
(summarized in Table 2). The results from both experiments (marked by ‘‘E’’) and theoretic cal-
culations (marked by ‘‘T’’) indicate that single- or few-layer Mo and W dichalcogenides are satisfactory
for electronic devises. In addition, the abundance of Mo and W dichalcogenides also makes them pos-
sible for industrial application with a low cost.
Fig. 17. Summary of the calculation results of stability of MX2 (M = transition metal atoms, X = chalcogen atoms) compounds.
(The lower-lying structure in each box (H or T) is the most stable phase and the upper-lying structure is the less stable phase.
White color means only one phase is stable. Orange color indicates 1H phase and Green color indicates 1T phase. Gray color
means neither 1T nor 1H phase is stable. ‘‘+’’ means half-metal; ‘‘⁄’’ means metal and ‘‘⁄⁄’’ means semiconductor.) Reprinted
from Ref. [308] with permission of ACS Publishers.
Table 2
Summary of band gaps of single-layer (1L), few-layer (fL) and bulk Mo and W dichalcogenides (E = experimental result,
T = theoretical calculation result).
S (eV) Se (eV) Te (eV)

Mo 1L: 1.89 (E) [23] 1L: 1.5 (T) [313] 1L: 1.1 (T) [313]
fL: 1.54 (E) [36] fL: 1.34 (E) [36] fL: 1.02 (E) [314]
Bulk: 1.2 (E) [312] Bulk: 1.1 (E) [312] Bulk: 1.0 (E) [315]
W 1L: 2.1 (T), 1.9 (T) [313,316] 1L: 1.7 (T) [318] 1L: 1.1 (T) [318]
fL: 1.57 (T) [317] fL: 1.43 (T) [317] 1L: 0.95, 0.75 (T) [319,320]
Bulk: 1.4 (E) [312] Bulk: 1.2 (E) [312]
8.1.1. Synthesis of TMD layers (MoS2 and WS2)

8.1.1.1. Top-down methods. Top-down methods are the methods to get single- or few-layers of TMDs
from their corresponding bulk materials. The most common top-down method is mechanical exfolia-
tion. Single-layer molybdenum and tungsten dichalcogenides have been successfully exfoliated by
adhesive tapes [224]. This method provides the highest quality single layer MX2. However, the
mechanical exfoliation is difficult to scale up and the reproducibility is low. Another top-down method
is thermal ablation by lasers [321]. Single-layer MoS2 can be obtained by this method, but the use of
lasers hindered the scale-up process.
The third top-down method is lithium intercalation, which can be traced back to 1975 [322]. Single
layer of MoS2 [323], WS2 [324], MoSe2 [325] has been obtained by lithium intercalation with high
yield, but the product loses the semiconductor properties as it changes phase to the metallic phase.
The semiconductor phase would be recovered by heating at 300 °C. Since this method needs reaction
for several days, modifying this method by electrochemical cell was used to make it more efficient
[326]. However, the flammability of lithium and the requirement of an inert atmosphere are still
challenging this method. Liquid exfoliation by direct sonication in different solvents has also been
studied, such as in organic solvents [107], mixed solvent of water and ethanol [327], aqueous surfac-
tant solutions [327] and a mixture of solvent and polymer [328]. This method is easy to carry out, but
the yield is very low.
8.1.1.2. Bottom-up methods. Bottom-up methods are the methods to get single- or few- layer TMDs
from the molecules or atoms. The most common method is chemical vapor deposition (CVD).
Several CVD methods for large-scale MoS2 ultrathin films have been reported recently. A typical pro-
cess follows these two steps: first, different Mo and sulfur precursors are heated to a high temperature
to let them evaporate; second, products deposit on the substrates at the cold zone. For example, MoO3
and sulfur powder [329], MoCl5 and sulfur powder [330], one precursor (NH4)2MoS4 containing both
molybdenum and sulfur [331], or molybdenum metal thin film on a substrate and sulfur powder [45]
have been used. The products of these methods are all polycrystalline single- or few-layer MX2 with
grain size 10–30 nm [45,329,330]. Recently, the mechanism of the CVD method by MoO3 and sulfur
powder has been systematically studied [332], showing that the nucleation concentration was higher
near the grain boundaries. The precursor concentration and the chamber pressure played key roles in
controlling the quality of the product. By modifying the process, the CVD method using MoO3 ribbons
as a precursor can produce single- or few-layer MoS2 on the micrometer scale.
8.1.2. Physical properties of MoS2 and WS2

The TMD layered structure is comparable to that of graphite and every single layer has a thickness
of 0.6–0.7 nm with strong covalent bond toward in-plane and weak van der Walls interactions toward
out-of-plane. A diagram of the lattice structure of MoS2 shows that Mo atom is covalently bonded to S
forming a single layer where Mo sits in the center and S at the edges [334]. Each subsequent layer is
only weakly bonded to surrounding layers by electrostatic dipole forces known as van der Waals. Due
to the weak bonds between the layers, it is possible to reduce them down to 2D sheets featuring few to
single individual layer known as a mono layer. Bulk Mo and W dichalcogenides have a variety of stack-
ing polytypes. The most common three are the 1T, 2H and 3R phases (as shown in Fig. 18a–c). The 1T
Fig. 18. The structures of the (a) 2H, (b) 3R and (c) 1T phases of molybdenum and tungsten dichalcogenides. The metal atoms
(M) are gray and the chalcogen atoms (X) are yellow [21], (d) 1H and (e) 1T phases of single layer molybdenum and tungsten
dichalcogenides [333]. The metal atoms are purple and the chalcogen atoms are yellow). Calculated band structure of bulk and
single-layer (f) MoS2 and (g) WS2 (the 2H phase for bulk and the 1H phase for single-layer materials). The black arrows indicate
the lowest energy transition [21]. Reprinted by permission of Nature Publishing Group.
phase has a tetragonal symmetry with octahedral coordination; the 2H phase has a hexagonal symme-
try with trigonal prismatic coordination; and the 3R phase has a rhombohedral symmetry with trigo-
nal prismatic coordination. The 2H phase is the most stable phase for MoS2. As the number of layers
decreases by one, there is no variety of stacking different layers. Thus, single-layer Mo and W dichalco-
genides only have two phases, 1H and 1T. The coordination of metal atoms is trigonal prismatic in the
1H phase and octahedral in the 1T phase (Fig. 18d and e). The 1H phase is the most common phase for
molybdenum and tungsten dichalcogenides. According to the calculation result in Fig. 18, the 1H
phase is the only stable phase for Mo and W dichalcogenides. Experimentally, the 1T phase can also
be obtained by lithium intercalation [33]. Both the 1T and the 1H phases have been found in the
lithium intercalation product. The 1H and 1T phases of Mo and W dichalcogenides have a similar
thickness of around 6–7 Å [333].
The lattice constant of MoS2 is 3.131 Å at 77 K [335]. A single S–Mo–S layer is 6.5 Å thick and can be
easily cleaved off bulk crystal using top-down processes such as the micromechanical cleavage tech-
nique [118,224] used with graphene, lithium-based intercalation [323] liquid phase exfoliation [107],
or grown with bottom up process such as CVD using Mo and S precursors [45,329,331]. The electrical
properties of TMDs are influenced by the number of layers because of quantum confinement effects
and change in symmetry. From bulk to single layer, the band gaps of MoS2 and WS2 change from indi-
rect to direct as shown in Fig. 18f and g. Bulk MoS2 exhibits an indirect band gap of 1.2 eV [336], which
gradually increases to a direct band gap [23,219,316,337] of 1.8 eV [23] as the number of layers
decreases to a single layer as a result of quantum confinement [316]. Bulk MoS2 and WS2 have indirect
band gaps from the C point to the point between K and C points in Brillouin zone. While, in the case of
single-layer MoS2 and WS2, the direct band gap is located at the K point. There are also indirect band
gaps in single-layer MoS2 and WS2, from the C point to the K point. In both the bulk and the single-
layer MoS2 and WS2, the valence band maximum (VBM) and the conduction band minimum (CBM) are
derived from the hybridization of Mo 4d orbital and S 3p orbital. In bulk MoS2 and WS2, the VBM at the
C point is formed by Mo 4d2z and S 3zp orbitals [339]. In single-layer MoS2 and WS2, the VBM at the K
point is formed by Mo 4dx2y2, Mo 4dxy and S 3px, S 3py orbitals (Fig. 19b) [340,341]. The absolute band
positions of the 1H phase single-layer molybdenum and tungsten dichalcogenides have also been calcu-
lated (Fig. 19a) [319]. From this result, single-layer can do something that bulk material cannot due to
the band positions. For example, bulk MoS2 is not suitable for water splitting, while single-layer MoS2
can be used for water splitting.
Lattice Strain plays an important role in modifying the lattice constants of a crystalline solid and
decreases the crystal symmetry, leading to important modifications in the energy band edges.
Strain engineering was proposed to enhance electronic device performance by modulating the strain
in the transport channel in complementary metal oxide semiconductor (CMOS) [342]. The applied
strain can improve charge carrier mobility (electron or hole), and thereby conductivity through the
channel. This technique has been employed by major processor manufactures, like Intel, IBM, and
AMD.
Introducing strain in the material can modify and improve the structural, optical and electronic
properties of graphene and any TMD layers are an emerging field [338,343,344]. Compared to gra-
phene, MoS2 is a more attractive material for elastic strain engineering because it is a semiconductor.
With measurements of optical absorption, photoluminescence, and photoconductivity, researchers
first experimentally studied the band structure of 2D MoS2 (1–6 layers), and measured a 1.9 eV band-
gap in monolayer MoS2 after a 0.6 eV upward shift in indirect bandgap energy from bulk MoS2 with
the decreasing of few layers [23] and also found that the luminescence intensity in freestanding
monolayer is much higher than supported MoS2 with an increase in luminescence quantum efficiency
by a factor of 104. Same group studied the band structure of monolayer MoS2 further with a support
and back gated MoS2 monolayer on SiO2/Si substrate. In this way, the doping level of the monolayer
MoS2 sample can be controlled by the back gate with a nearly undoped level when applying a 100 V
gate voltage. After the first experimental study of electronic band structure of MoS2, it is proposed in
many theoretical papers [345–347], that mechanical strains can strongly perturb the band structure in
2D MoS2. This was immediately followed by the experimental verifications has been reported [338]. In
this work, they exfoliated monolayer and bilayers MoS2 on a layer of cross-linked SU8 photoresist
deposited on polycarbonate (PC) beam, and by bending the PC beam with a four point bending
Fig. 19. (a) Calculated band alignment of single layer 1H phase MX2 (vs. Vacuum). Solid lines by PBE and dashed lines by HSE.
(b) The origin of conduction band minimum and valence band maximum in MX2 [319]. (c) Schematic of the beam bending
apparatus used to strain MoS2. (d) Photograph of bending instrument with MoS2 under strain. (e and f) Direct to indirect band
gap transition in MoS2. (e) The intensity of the peak of strained monolayer MoS2 (solid shapes) with a fit (dashed curve) to the
rate equations consistent with a degenerate direct and indirect optical band gap at 1.3 ± 0.6% strain. PL intensity of bilayer peak
(unfilled circles) with no measurable change in intensity. Each color represents a distinct device. (f) The fundamental band gaps
of strained monolayer MoS2, with an expected degeneracy at 5% strain. Optical band gap calculated by including the exciton
binding energy yields a degeneracy at 0.1% [338]. Reprinted by permission of AIP Publishers and ACS Publishers.
apparatus they applied uniaxial strain to the MoS2 flakes (see Fig. 19e and f). The amount of uniaxial
strain applied are calculated from the bending and verified with Raman and PL spectra. In all previous
reports, we can assume the strain over the MoS2 samples is uniform [348,349]. The researchers
applied local uniaxial strain up to 2.5% in 3–4 layers MoS2 by buckling the flake on elastomer [321].
One advantage of this measurement set up is to achieve large amounts of data with different strain
values at once. The overall tuning rate of direct bandgap is close to what others measured, but the fit-
ting and analysis of the data favors a nonlinear tuning rate starting with a large tuning rate at very
small strain, which decreases with the increase of strain applied. Other than uniaxial strains, other
researchers applied compressive biaxial strain on trilayers MoS2 instead to a piezoelectric substrate
[350]. Due to the limit of the piezoelectric substrate, the maximum strain applied is only 0.2%. They
claimed exceptional tunability from the experiment of 300 meV/% red shift rate.
Furthermore, the unique properties of TMD anticipate for using a new state variable, namely valley
quantum numbers, for logic operations in suspect valleytronic devices [351]. Previously, the valley
parameter had been retrieved by applying magnetic field or stain in non-TMD materials: however,
the TMDs properties allow access to valley parameter by circularly polarized light. Theoretical cal-
culations show that strong spin–orbit coupling causes the valance band at the energy minima’s of
the first Brillouin zone to split opposite to each other. This gives rise to a coupling between the valley
parameter and spin, and two valleys of the same energy, but with different momentum values
[21,333,352,353]. Incoming polarized photons interact with the spin of the holes, pushing them
preferentially into one of the two valleys. This valley polarization is preserved during subsequent
recombination resulting in the emission of polarized photons, which allows for the formation of val-
leytronic devices [333]. Recently, several researchers have demonstrated exclusive valley population
via exciting edge electrons with circularly polarized light in monolayers of MoS2 and WSe2 [354,355].
Quantum confinement effects and optical properties of the electronic structure of MoS2 have well
known and noticed in thin films as well as in nanoplates and nanotubes [356]. In particular, earlier
report [219] shows the development of photoluminescence in a few layers of MoS2. It showed that
MoS2 photoluminescence increased with layer thickness, and the luminescence from a single-layer
was the strongest though it was absent in bulk material. The cause of this luminescence performance
is because MoS2 changes into a direct bandgap semiconductor while reduced to a single-layer. In
Fig. 20, it is reported that photoluminescence spectra of different layers, and bulk MoS2. In bulk
MoS2, no photoluminescence is present while for MoS2 monolayer, the Raman and photoluminescence
intensities show a dependence of layer thickness. In addition, the Raman spectra of MoS2 layers sug-
gest that the phonon structure is also responsive to the available layers and strain besides carrier con-
centration and temperature [217]. Recent studies recommend that optical transitions in monolayer
TMDs are controlled via excitons instead of direct interband transitions [219,334]. For instance, the
optical absorption spectra of both mono- and bi-layer MoS2 exhibit two distinct peaks and the exciton
binding energy could be very high (0.5–0.9 eV) for single-layer and low (0.4 eV) for a few-layers
[219].
Fig. 20. Photoluminescence and Raman spectra of MoS2 monolayer, bilayer, hexalayer, and bulk sample. Reprinted from Ref.
[219] with permission of ACS Publishers.
STM studies have been performed on MoS2 nanoparticles on Au(1 1 1) [357,358]. It was found that
MoS2 forms triangular nanoparticles with sulfur termination edges. These edge sulfur atoms are
shifted half the lattice constant [236,359] and there is a propensity for them to form S2 dimmers, giv-
ing rise to higher occurrences of nanoclusters having an even number of edge sulfur atoms [358,359].
These sulfur atoms at the edge and corners of the nanoparticles, or rather, their vacancies, pose as
active sites for the absorption of sulfur, making it useful as a catalyst for desulfurization in the petro-
chemical industry. The unique lattice vibration properties and electronic band structure of TMDs sug-
gest new openings for electronic and optoelectronic devices.
8.1.3. Functionalization of TMDs

One very important aspect of organic chemistry is functionalization. By adding functional groups to
an organic molecule, the properties of the molecule can be significantly changed. The same principles
as for carbon-based organic molecules can be applied to any 2D layers [360]. By adding functional
groups to the TMDs, both chemical and physical properties can be tuned. The effect of defects or
impurities on the properties has been explored by first principles calculations for both non-magnetic
and semiconducting 2D MoS2 [361,362]. For instance, it has been reported that substitution of the V
and Fe for S atoms on the MoS2 surface increases a magnetic moment and also doping of Au or Pd
induces a magnetic moment on the MoS2 surface [363]. Considered that in nonmetallic materials mag-
netism created on the sp orbitals produces robust long-range exchange coupling interactions com-
pared to the d and f orbitals of the transition metal atoms, it has been reported that magnetic and
electronic properties of N-, B-, H-, O-, F- and C-engrossed MoS2 single layer [364]. The theoretical
investigation revealed that the N and H atoms in the single layer MoS2 that engrossed onto the S atoms
contributes to p- and n-type semiconducting properties, respectively. On the other hand F- and H-en-
grossed MoS2 single layers produces long-range antiferromagnetic properties. In the same way, long-
range antiferromagnetic properties showed in H-engrossed MoSe2, MoTe2 and WS2 single layers and
F-engrossed MoSe2 and WS2 single layers [365]. Tuning the electrical properties of single layer MoS2
via defect engineering have been explored by oxygen plasma treatment [366,367].
First principles plane-wave calculations showed that the functionalization of TMD structures by
adatom adsorption (for example, Cr, Fe, Ni, Mo, O, Pt, Ti, Ge, Si, and V) and formation of vacancy defects
(single, double and triple vacancies in TMDs) [368]. It was shown that local magnetic moments could
be achieved by the adsorption of particular transition-metal atoms besides Si and Ge atoms. In the
case of vacancy defects, only triple vacancy generated in single layer MoS2 which accelerated a mag-
netic properties, while other vacancy defects have not induced any magnetic properties. On the other
hand, in semiconducting MoTe2, WS2 and MoSe2, single vacancy induced long-range antiferromagnetic
properties [365]. It has been reported that isotropic strain also increased the magnetic properties of
the single layer MX2, particularly for Se and S nanosheets. It was shown that magnetic moment pro-
duced by strain was associated with stronger ionic-covalent bonds. On the other hand, magnetic cou-
pling strength variation and ferromagnetism associated with the strain were assumed to develop from
the effects of through-space and through-bond interaction [369]. The magnetic property present in
single layer MX2 is entirely different from graphene layers [370]. These functionalization studies
recommend the opportunity of using TMDs in spintronics and nanoelectronics applications.
8.1.4. Applications of MoS2 and WS2

Digital electronic circuits are contained many different assemblies of logic gate, each logic gates
usually consists of few transistors. The metal–oxide–semiconductor field-effect transistor (MOSFET)
is the basic component for most digital electronic circuits. There are three key factors for materials
used to make digital logic devices: high charge carrier mobility for fast operation, high on/off ratio
(104–107) for effective switching and low off-state conductance for low power consuming [371].
1–2 eV band gaps of Mo and W dichalcogenides can provide high on/off ratio [118] with low power
dissipation. MoS2 is the first candidate to be studied because of its semiconductor band gap and high
tensile strength, which gives it possible potential for many applications. The first literature of
single-layered MoS2 shows the mobility of 0.5–3 cm2 V1 S1 range [224], are too low for a real devices
application. In the light of this, MoS2 nanopatches was prepared by mechanical peeling, with high
field-effect mobility in tens of cm2/vs and an on/off ratio higher than 105 [372].
State of the art MoS2 top-gated field effect transistor (FET) developed recently and showed excep-
tional on/off current ratio up to 108, room temperature mobility of >200 cm2 V1 s1, and sub-thresh-
old swing of 74 mV per decade [118]. In the same way, recently, another group [373] used a hafnium
oxide as the dielectric layers to show a room-temperature single-layer MoS2 mobility of at least
200 cm2 V1 s1, which is comparable with graphene nanoribbons, the on/off ratio of current is
1 108 (Fig. 21). The top-gated geometry with high k dielectric used allows a reduction of working
voltages, therefore MoS2 can be considered as a good candidate for low-power electronics. It has also
demonstrated ultra-sensitivity of 880 A/W at a wavelength of 561 nm in monolayer MoS2 photodec-
tors with the photoresponsivity ranging from 400 nm and 680 nm [374]. The result shows great
potential for application of MoS2-based integrated in light sensing, optoelectronic circuits, video
recording, biomedical imaging, and spectroscopy. On the other hand, single layer MoS2 is also a good
material for flexible electronic/optoelectronics. Its in-plane stiffness is 180 N/m, accompanying to an
effective Young’s modulus of 270 Gpa, equivalent to that of steel. Breaking arises at an effective strain
between 6% and 11% [375]. Single-layer MoS2 amplifier [376] and logic operations [377] have also
been demonstrated. Even though one might argue that its mechanical property is not as exceptional
as graphene, it is adequate for flexible electronics/optoelectronics applications.
However, the high mobility is still controversial. Dielectric environment (e.g. HfO2) influence the
mobility a lot due to the screening effect of the impurities in single- or few layer MoS2. [373] The
mobility can be over stimulated by 10–50 times due to the increase of capacitive coupling of the chan-
nel by the dielectric of the top-gate to the back-gate. The carrier mobility of single- or few-layer MoS2
FETs on SiO2/Si substrate (SiO2 as gate) was only 10 cm2 V1 S1 without the high-k environment at
room temperature [378]. The interface between MoS2 and SiO2 has been considered as one of the main
limit [379]. The mobility has been increased to 200 or 500 cm2 V1 S1 by HfO2 [118] or Al2O3 [380]
top-gate due to the high-k dielectric screening charged impurities. On the other hand, mobility of
MoS2 FETs has also been underestimated, which is caused by the Schottky barriers at the interface
of MoS2 and metal contacts [373,381]. The mobility was enhanced from 100 to 220 cm2 V1 S1
by reducing the contact resistance and thinning the Schoottky barrier [382]. Overall, the mobility of
single- or few-layer MoS2 FETs should have a high mobility and the FETs are quite promising for
new electronics. Additionally, CVD grown MoS2 films have good mechanical strength for flexible
Fig. 21. (A–C) Preparation process of single-layer MoS2 transistor, (D and E) the gate control of single-layer MoS2 transistor.
Reprinted from Ref. [118] with permission of Nature Publishers.
devices, which has been demonstrated by making FET on flexible polyimide substrates [383]. Single-
and few-layer MoS2 films also have a lot of other applications, such as photodetecting [384] and gas
sensing [385]. Because of the direct band gap of single layer, MoS2 has also been employed for
photocatalytic [386,387] and photovoltaic [217,339,388] applications due to the high absorption in
the solar spectrum region.
8.2. Hexagonal Boron Nitride (h-BN)
Boron Nitride (BN) is a synthetic compound discovered earlier [389] with the reaction of boric
oxide and potassium cyanide. However, industrial uses for BN were not realized for another 100 years
[390]. The microcrystalline powder form of BN has many uses as a lubricant or coating when chemical
inertness at high temperature is required. BN powder is also used extensively as a filler material and
precursor for other boron compounds. The hot-pressed form of boron nitride is especially used as a
refractory material. Properties like its high thermal conductivity, high thermal shock resistance, and
machining ease, make this BN invaluable in furnaces, reactors, and other high-temperature applica-
tions [391].
BN is assumed to be many crystalline phases, of which hexagonal (h-BN) including boron nitride
nanosheets (BNNS) and cubic (c-BN) films are most common. [37,124,392] c-BN is similar like dia-
mond because of high chemical resistance, best electrical insulating material having excellent hard-
ness. This c-BN material can be replaced with carbon in many different applications because carbon
materials are limited by the use of oxidation. Also, this indirect band gap c-BN could be impregnated
with berkelium or silicon to develop p-type and n-type high temperature semiconductors.
Additionally, it is unreactive material with ferrous metals at high temperature as 1500–1600 K.
With the similar crystalline structure of graphene, BNNS has been studied as the most outstanding
material of 2D category [121,394]. BNNSs are 2D wide band gap (5.9 eV) [121] semiconductor lay-
ered material happening in hexagonal structure exclusively made of constant boron (B) and nitrogen
(N) atoms which build a specific honey-comb structure of B3–N3 hexagon [395,396]. h-BN is a soft, low
density modification of BN and is composed of layers of flat six-atom sp2-hybridized hexagonal rings
(three atoms boron and three atoms nitrogen alternating) with the rings stacked perfectly atop each
other in alternating fashion. The spacing between two successive layers is 0.334 nm, which is similar
to that of graphene (0.333 nm). In the meanwhile inside a layer, the bond length between two succes-
sive B and the N atoms is 1.44 Å (Fig. 22a and b) [393]. Due to the similar crystal structure to graphene,
BNNS also develop huge potential in the progress of corresponding composite and electronic devices.
For instance, BNNS have been used as a substrate and dielectric materials for developing a graphene-
based electronic devices due to the smooth surface that is comparatively absence of charge traps and
dangling bonds [397]. The outstanding chemical and thermal stability, and excellent oxidation resis-
tive properties, will lead this materials in a while to the innovative solicitations in extraordinary effi-
cient nano-electronic devices. The intra-layer interactions between the single layer BNNSs are
frequently well described. These interactions between the layers are found out via a subtle balance
Fig. 22. (a and b) Graphite and hexagonal boron nitride stacking sequence and lattice parameters. Adapted from Ref. [393] with
permission of Nature Publishers.
between dispersion forces, Pauli repulsions, and electrostatic interactions. It is important to under-
stand these interactions for the essential features of their structural, mechanical, and electronic prop-
erties as well as for the new materials to design with desire functionality.
8.2.1. Synthesis of BN
Bulk BN has been used to synthesis BN monolayer by either chemical solution based methods, or
mechanical cleavage [398]. The flake size is typically imperfect, which can delay the potential applica-
tion of h-BN. Numerous alternate synthetic methods, for e.g. CVD [399–401] and PVD [402,403] have
also been established. These synthetic methods are complex, time consuming and small yield of prod-
ucts. Earlier it was established that well-ordered h-BN single layer can be achieved via borazine
expose to metal surfaces at elevated temperatures (>700 °C) [404]. Still, this technique needs ultra-
high vacuum (UHV). On the other hand, this UHV technique is good in preparing single layer h-BN,
it is difficult to prepare multilayers [336]. For the electronic uses, it is essential to make high quality,
well-ordered and large area BNNSs layer structure at very low substrate temperature with con-
siderable vacuum levels. As yet, it is a challenge to produce high quality BNNSs with large quantity
at low vacuum and low substrate temperature.
8.2.2. Physical properties of BNNS

In BNNS, contiguous sheets vary in stacking arrangements of atomic layers with respect to carbon
atoms in few layer graphene (Fig. 23a and b). Generally, h-BN can have an equally long-range order,
Fig. 23. (a) Current–voltage (I–V) characteristics of as-grown BNC with different percentages in carbon measured at room
temperature. (b) The drain current as a function of the voltage applied to the back gate for a 7-lm-wide BNC ribbon with 40%
carbon. The drain–source voltage is fixed to 1 V [448]. (c) I–V characteristic curves of single layer graphene placed on SiO2 and
BNNSs under ambient conditions (insert: schematic of the graphene device structure with grown h-BN nanosheets [449].
Reprinted by permission of Nature Publishers and ACS Publishers.
but the layered planes of h-BN are translated parallel to each other while maintaining boron-nitrogen-
boron stacking sequence among layers (ABCABC). The meaning of long-range order in h-BN is that all
layers are parallel and appropriately oriented with respect to the c-axis [405]. This exceedingly steady
and mechanically robust structure shows tremendous resistance to oxidation, and chemical stability
in anticipation of over 800 °C temperature. Therefore fabricating BNNS is very attractive for many
applications in the bulk level where structural integrity and chemical stability are desired. Thus, it
is mainly exciting to start the chemical reaction with atoms involve in the bulk BN lattice while hold-
ing the same materials essential properties. The current improvements in the field of 2D layers, it has
become evident that for the solicitation of BNNSs, substitute chemical approaches would be essential
to incorporate and exploit BNNSs in various applications including nanocomposites and surface coat-
ing [229].
BN nanostructures are easily comparable with carbon nanostructures as explained earlier.
Monolayer system is getting an excellent research interest between all other existing nanostructures
[401,405]. For emerging development in recent technology, it is helpful to have mono layer structures
which are passive, stay clean at closed circumstances and are stable at higher temperatures. Due to a
structural analogue of graphene, Mono layer BNNSs are promising for many applications [401]. An
atom thick BN nanosheets offers an unusual properties which cannot be recognized in graphene lay-
ers: such as high optical transparency [406], large band gap [407], high mechanical strength [398],
tunable photoluminescence [408], UV cathodoluminescence [409], atom-thick electron tunneling bar-
rier [410] and high thermal conductivity [411]. It is prominent thermochemical stability (stable up to
1000 °C in air) [412], makes it a greater material for high-temperature applications. Additionally, it is a
great material in chemically-hazardous environment [413] because of the chemically-passive nature
and strong bonding. In addition, nano-carbon in which non-polar C–C bonds create an even and
smooth sidewall structure, whereas BNNS contains polar B–N bonds using ionic character, which
can encourage an additional dipole moment inside the structure, representing BNNS material is
undoubtedly greater to nano-carbon materials.
Monolayer BN has a solid impact on the physicochemical properties of a materials binding and
bonding of atoms and molecules could vary by orders of magnitude, in addition to the charge trans-
port properties parallel and diagonal to the boundary. However, owing to the electronegativity
changes among those two atoms (B and N), the electrons has a tendency to restrict nearby the N
atomic centers consequently making an insulating material. Moreover, the opposition of those two
bonds (B and N) leads to characteristic charges near the atomic centers, hence permitting for monopo-
lar inter-layer electrostatic connections to connect higher electrostatic multipoles, Pauli repulsion, and
dispersion interaction in prescribing the interlayer binding nature. It is successively, stabilizes the AA’
assembling mode, whereas a boron atom assuming a limited positive charge in single layer placed on
top most of the oppositely charged nitrogen atoms in the neighboring layers.
According to the earlier established concerns, any one might usually assume that electrostatic con-
nections among moderately charged atomic interiors can play an important role in the polar layered
structures. Particularly, the electrostatic interaction between those two different charges of atomic
centers in neighboring BN layer structures are predicted to affect in a substantially smaller inter-layer
distance than graphite. However, the inter-layer distances in graphite (3.33–3.35 Å) [393] and in BNNS
(3.30–3.33 Å) [414] are basically the same proposing that monopolar electrostatic interaction, which
present in h-BN and are lacking in graphite, have an affect on the inter-layer binding. This effect is
dependable with a report explaining that van der Waals forces are more responsible for attaching lay-
ers at the suitable inter-layer distance, rather than electrostatic interactions [415].
8.2.3. Wide band gap modification

There is a limitation of using wide band-gap of BNNS samples for real electronic applications due to
the ionic bonding between B and N, BNNSs are electrically insulating, with a large electronic band gap
(4.6 eV) [416,417]. The electrical resistivity of BNNSs are 1017 and 104 X cm at room temperature
and at 200 °C, respectively [418]. In order to accomplish preferred electronic properties, for instance,
to develop a practical transistor or diode, it is necessary to do a doping of BNNSs layers and stimulate
impurities in the electronic structure [415]. Till now, doping is a greatest possible process to recreate
the energy band gap in the corresponding material. The doping method could be achieved by plasma
ion implantation method [419]. The atoms from doping materials combine with the BNNSs that may
be possible to lead the construction of many different layered structures and develop the semiconduc-
tor properties for electronic applications [419].
Generally, BNNS samples may be doped with beryllium to obtain p-type and sulfur, boron, carbon,
nitrogen, and silicon for n-type materials [420]. However, identification of the best doping concentra-
tions in BNNS sample is still under investigation. As yet, it is stated that the mixture of C atoms with
BN may possibly extend to the development of diverse (Bx–Cy–Nz) layered materials. Theoretical
analysis has predicted that the electronic and band structure of Bx–Cy–Nz are depend on electronic
and composition prearrangement of B, C, and N components within the lattice [420]. This incorporated
dopants in the crystalline structure will improve the semiconductor and electronic properties of the
material (see Fig. 23a and b). Many other possible structures might be constructed by doping in
BNNS layers. As we know that integrated circuits of advanced semiconductor devices are smaller than
20 nm in width and length, and it will be reduced further in future. In that small size, doping of a sin-
gle atom in the device can drastically change the device behavior. A single B3–N3 ring could be hybri-
dized into several possible ways, for instance B2–C2–N2, B1–C3–N2, B2–C3–N1, B3–C1–N2, etc. [421,422]
8.2.4. Thermal conductivity of BNNS

Regardless of inconsistencies in the real numbers anticipated under various models [423–425], the
consent is that the h-BN nanostructures are exceptional thermal conductors even though they are
electrically insulating. The BNNS thermal conductivity (k) is 2000 W m1 K1 [418]. CNTs and gra-
phene are thermally and electrically conductive, therefore cannot be used in thermal management
of electronic materials [426]. It has been proposed that a single layer BNNS contains a greater k value
compare to multiple layered samples because of contract interlayer phonon scattering. The thermal
conductivity reduction with multiple layers ultimately converging to the h-BN value [425].
Investigated results from direct analysis of BNNSs thermal conductivity values are not widely known.
Earlier reported value of an in-plane is 40 W m1 K1 for a bulk BNNS material which was developed
in a top of filter membrane [418]. Because of the insignificant BNNS adjacent sizes (less than 1 mm),
this value is apparently far away from the exact k for a separate single layer BNNS owing to the impor-
tant phonon scattering inside the bulk material. However, important thermal conductivity improve-
ment of polymer composites with BNNS filler has been reported [427,428]. Since BNNSs are
electrically insulating and thermally conductive, BNNSs composite can be used in thermal manage-
ment of high power electronics. In presence of BNNSs the thermal conductivity of nanofibrillated cel-
lulose (NFC) increases from 0.035 W m1 K1 to 26.2 W m1 K1 while loading by 5% of nanofiller
[426]. For applications such as high-speed electronics and dielectroincs, a material with property of
quick heat releasing as well as electrical insulation is necessary. BNNSs can be used as nanofiller in
polymer materials to improve the thermal stability, thermal conductivity, and dielectric properties
in polymeric composites. For an example, the dielectric constant increases with BNNSs loading in
polymer composite of poly(methyl methacrylate) (PMMA) [429].
8.2.5. Mechanical property of BNNS

As we know that single layer defect free graphene is the strongest material [124]. This was antici-
pated that the single layer BNNSs are equally stronger like graphene because of similar structure and
also stronger than any other 2D nanostructured materials [430–433]. One of the previous study
demonstrates that the in-plane strength of a single layer BNNS and graphene are 267 N/m and
335 N/m, respectively [433]. Thus, BNNSs could be wonderful reinforcing fillers like graphene for poly-
mer composites. Mostly nanoindentation technique has been used to measure the mechanical prop-
erty of the few-layered BNNSs and graphene [124,399]. As we mentioned earlier that the
nanosheets are very flexible, it can be easily broken with deflections of 70 nm using the diamond
indentation tip. Researchers have reported that the breaking stress and modulus of few nanometer
thickness BNNSs were in the array of 8–16 N/m and 220–510 N/m and, respectively. In view of the
few layer nanosheets, these estimates were slightly lower than anticipated. To the presence of intrin-
sic vacancy defects in BNNSs, previous studies ascribed the lower mechanical performance. Truly, sim-
ulation results also showed that both breaking strength and modulus of BNNSs reduced with the
vacancy concentrations [399]. In another case, sonication assisted solvent exfoliation of BNNSs with
thickness between 25 and 300 nm were showed that flexibility of the nanosheets improved with
reduced thickness. This observation was ascribed to the defect induced stacking faults among the lay-
ers [434].
The tribological or friction properties of BNNSs are also fascinating because of similar quality
appearance to many other 2D NSMs. As we know that, similar like bulk graphite, h-BN also extensively
used lubricant material because of the weak forces keeping the nearer planes within their structures. A
friction force microscopy study on few layers also suggested that the frictional characteristics of gra-
phene, BNNSs, and other 2D nanostructured materials are thickness dependent [435]. The thin
nanosheets showed greater frictions because of improved susceptibility to outside of plane deforma-
tion. Very recently, researchers have reported that the friction force might accelerate flexible, dynamic
wrinkling on the top most layer for different types of nanosheets including graphene, BNNSs and most
of TMD layers [436].
8.2.6. Functionalization of BNNS

Functionalization has been proven as an effective way to exfoliate CNT [437,438], graphite [439]
and BNNT [440] by defeat the van der Waals forces that clench the whole unit together. Similarly,
functionalization approaches are very effective in overcoming the intra layer interactions among
the h-BN single layers achieve exfoliation. The chemical functionalization has been studied extensively
with a view of tuning the band gap, particularly for graphene [441–443]. This graphene study has
encouraged robust interest in the functionalization of BNNS. As we described earlier that bulk h-BN
is an insulator with a band gap value of 5.69 eV [444]. The band gap of the CVD grown BNNS was
observed as 6.07 eV. This band gap variation is due to the lack of inter-layer coupling [401].
Density functional theory (DFT) and first principle calculations showed that hydrogen atom can be
linked to both sides of B and N atom, and the band gap of this hydrogenated BNNS is reduced to
3.05 eV [445].
First principles plane-wave calculations have been used to investigate the physical properties of
functionalized BNNS by adatom adsorption [446]. Many different atoms have been considered for this
calculation, such as Fe, Si, C, Pt, Cu, Ni, V, O, Pd, Ti, Sc, B, and Si, and also found that some atoms could
not bind to a BNNS, such as Zn, Ca, N, H, W, Cr, Mo, and Mn. It has been shown that the magnetic prop-
erties of insulating BNNS could be tuned by selecting the specific adatoms. And also, it has been
showed that a wide band gap value was reduced considerably when B or C added to BNNS, this reduc-
tion is due to a reconstruction of their structure. Oxygen covered BNNS was determined to be a semi-
conductor with a small band gap and a metallic ferromagnet. Some of the adatoms did not affect the
band structure of BNNS significantly. According to DFT calculation, the charge transfer could occur
only between BNNS and either a donor or an acceptor [447]. This charge transfer significantly reduces
the band gap of BNNS and produce either an n- or p-type semiconductor based on a donor or an accep-
tor, respectively. The doping effect of BNNS has been explained in the Section 8.2.3.
8.2.7. Application of h-BN

h-BN has many novel advantageous physical properties, such as electrical insulation, high thermal
and chemical stability, high thermal conductivity, and excellent mechanical properties, all of which
entail applications in many fields.
BNNS layer structures have been used for numerous application, including electronic and optoelec-
tronics. For instance, BNNSs are believed an outstanding dielectric material. Additionally, BNNSs have
also been described as excellent substrates for graphene based electronic devices. Fig. 23 shows a sig-
nificant increase in output current recorded when graphene layers deposited on BNNSs substrate
[449]. In another example, a device from mechanically exfoliated single layer graphene placed on
BNNS substrates displayed high mobility as 60,000 cm2 V1 s1 [449]. It can be a productive coating
to prevent chemical attack by other materials; a boron diffusion source for silicon or a gate insulator
for field-effect transistor. With the advent of graphene field-effect transistors, h-BN has shown to be
an excellent gate dielectric and a substrate that provides a smooth and flat surface necessary for maxi-
mum carrier mobility in graphene sheets [450–452].
Deep UV (DUV) photo detectors are commonly applied in military and several commercial applica-
tions including pollution monitoring, environmental protection, protected space communications,
information storage technology, water purification, NASA spacecraft applications, flame sending and
quick missile plume detection [453]. Several wide band gap semiconductors which have better optical
properties including diamond [454], zinc oxide (ZnO) [455,456], doped gallium nitride (GaN)
[457,458], and silicon carbide (SiC) [459,460] have been used for UV detectors. However, there are
few concerns with BNNSs for DUV detectors, for example: BNNSs layers have large energy-band gaps,
thermally and chemically more stable than commercially available semiconductors which are used for
UV applications. The even and smooth surface of nanosheets has massive potential to absorb UV light
and convert it into a signal. Furthermore, BNNSs-associated DUV optical sensor demonstrate decent
reply to UV region with lower than 254 nm wavelengths, hence they can be used for aerospace com-
munication and devices functioning in extreme environments where other material properties fail to
meet (GaN, ZnO, and diamond). While visible light emitting diodes (LEDs) and laser diodes are well
established, materials for UV emission have only recently come of age. The III–V compound GaN is
a prominent material in violet laser diodes, and their most widespread use is to read discs in Blue-
ray players [461–463]. However, many UV applications exist in medicine, security/counterfeiting,
and antimicrobial/sterilization methods all of which could benefit from UV LEDs. UV emission from
h-BN has been reported with wavelengths between 215 nm and 227 nm depending on crystal quality
[406,416]. Since most UV devices still rely on conventional UV lamps, h-BN has potential to become a
dominant, low power solid-state UV emitter [407].
Intersection of a metal and semiconductors can be designed to create a Schottky barrier. Generally,
in diode, the metal region is the anode and n-type semiconductor is the cathode. Currently used con-
ventional cathodic materials are chromium, platinum, molybdenum, silicides and tungsten. The wide
band gap BNNS materials that might be used for Schottky diode after doping [420,464–466]. By means
of doped semiconductors, the depletion region width drops off. Lower than certain bandwidth, the
charge carriers could penetrate over the depletion region. The junction will not behave like a rectifier
at a high level of doping. This could be applied for instantaneous development of diodes and Ohmic
contact, starting point of diodes is between the silicide and the region of n-type dopants and the pro-
duction of Ohmic contact is in-between the metal and a heavy doped n- or p-type region in semicon-
ductor [466].
In recent times, graphene-related gas-sensors and nano-electronic devices [467,468] have been
used effectively that carried great attention to the nanotechnological device using BNNSs layers. BN
nanocrystals suggests the immense potential to increase an extensive sensitivity of the sensor for vari-
ous working gasses. The density functional theory calculation showed that boron nitride nanotubes
(BNNTs) and C-doped BNNTs can be used for gas sensing properties (for some small gas molecules
such as CO2, CH4, N2, H2, F2, O2, and NO2) [421,469–471]. But, BNNTs exist a low sensitivity to the sev-
eral gaseous molecules, while layered BNNSs are very attractive for high-performance gas-sensor
[413]. The chemical modification of B and N atoms induce the ionic nature of BN nanocrystal that
might be extremely sensitive for different gasses (CH4, H2, N2, etc.). Electronic properties of BNNSs
can also be affected strongly by slight interaction of small gas molecules on the surface which is more
essential for nanomaterial based gas-sensor. Even and smooth surface of BNNSs layers permit their
atoms completely to the adsorbing gas molecules, allowing larger sensor area per unit volume and
improve the sensitivity. Because of the high chemical inertness and thermal stability, this BNNNs
gas sensor can be used in tough environments where other material properties fail to meet [470].
h-BN can be used as support for catalysts. The popular materials used for catalysts are oxides
phases, such as silica, alumina, and silica-alumina mixture. To improve stability and catalytically
activity, other materials can be added which has high thermal conductivity and thermal stability, as
supports for catalytically active phases. Besides these features, BN has other attributes, such as high
surface area, hydrophobic (thus preventing moisture condensation on its surface) and weak chemical
support-active species interaction that leads to a possible good catalyst. It shows that porous BN sup-
port Pt–Sn catalysts were efficient catalysts for the selective a, b-unsaturated aldehyde hydrogenation
into unsaturated alcohol [472]. Although butanol and butyral-dehyde in crotonal-dehyde hydrogena-
tion are auspicious based on thermodynamic equilibrium, the product selectivity could be moved to
crotyl alcohol via adjusting the reaction kinetics on the Pt–Sn/BN catalysts. The crotyl alcohol yield
was 38%, which is very high on Pt–Sn (0.75)/BN at 80 °C. Furthermore, crotyl alcohol selectivity was
extended to 80% at a conversion of 10% close to 40 °C. Pd loaded-porous BN was proven to be a catalyst
that could be used under hard conditions, like methane oxidation or hydrocarbon cracking without
exhibiting any decrease in activity [473].
8.3. Silicene and germanene
Silicene and germanene are silicon and germanium based analogue of graphene which have been
studied theoretically long before the finding of room temperature stable and free standing monolayer
graphene [474]. Despite the similar electronic configuration for carbon, graphene is stable in sp2
hybridization thus formed honeycomb like structure, whereas silicone is more stable in sp3 hybridiza-
tion [475]. Therefore, a from thermodynamic point of view, it is presumed to be impossible to synthe-
size silicene spontaneously from Si atoms until researchers got the breakthrough in producing single
and multiwalled silicon nanotubes (SiNT) structures which have given the hope to the scientific com-
munity that graphene like structures from Si could be obtained [199,476,477]. Ab-initio calculations
have demonstrated that SiNT and CNT possess similar electronic properties [478]. However dissimi-
larity in the experimental results raises further doubts (due to the different process for synthesizing
SiNT and CNT) about the existence of Si in different form other than diamond until Nakoano et al.
chemically exfoliated Mg-doped Si layers of thickness <1 nm and lateral size 200–500 nm from Mg-
doped CaSi2 [199,479]. These layers were capped by oxygen, thus providing the stability when
exposed to oxygen. Presence of oxygen change the sp2 hybridization to sp3 and modify the chemical
and physical properties of Si nanosheets [480]. This oxidation of Si is facilitated by unstable Si–H
bonding leading to the aggregation of Si nanosheets thus limiting the choice of solvents and fab-
rication method [481]. It is reported in the literature that the oxygen free organic group functionalized
Si nanosheets have been synthesized by the chemical reaction of layered polysilane with organic sol-
vents such as n-decylamine and phenyl magnesium bromide (PhMgBr) [481,482]. As mentioned in the
Section 5 that chemical exfoliation of monolayers introduce irreversible defects in the nanosheets, Si
nanostructures have been synthesized by alternative methods mainly epitaxial adsorption of Si atoms
on metallic substrates (Au, Ag, Ir etc.) [150,151,195,196,483]. Among them Si/Ag and Ge/Ag system
have been studied extensively because both systems show phase separation tendency when Si and
Ge is adsorbed on Ag surface. Despite this tendency, Si and Ge have different solubility in Ag.
Whereas Si has very low solubility in Ag, solubility of Ge is relatively very high [484]. Therefore,
the diffusion of Si in Ag is negligible, thus, nanostructures of Si could be synthesized on Ag surface.
8.3.1. Structural and electronic properties of silicene and germanene

Complimentary to the 2D hexagonal honeycomb structure of graphene, first-principles total-en-
ergy calculations predict the corrugated aromatic stage (buckled honeycomb structure) for Si and
Ge 2D nanosheets [474]. It has demonstrated that the stability of low buckled (LB) honeycomb struc-
ture (DLB of 0.44 Å for Si and 0.64 Å for Ge) of Si and Ge nanosheets compared to high buckled (HB) and
planer (PL) honeycomb structure from first-principle calculations [485]. This stability of the low buck-
led structure is attributed to the reduction of Si–Si nearest-neighbor distance of 0.225 nm and
ambipolar nature of the system. Epitaxially grown silicene also shows evidence of LB structure
[150,151,205]. Charge density iso-surfaces of r- and p-bonding in PL and LB structure are shown in
Fig. 24a [486]. Stability of LB structure in Si and Ge monolayers is related to the weak p bonding of
perpendicular pz orbitals due to the increased bond length results in puckered structure. This height
difference causes the dehybridization of sp2 orbitals into sp3-like orbitals. First principle calculation
has also predicted the semi-metallic character of silicene and germanene due to the linear crossing
in the band structure at point K and K0 in LB structure (Fig. 24b) [485,486]. Silicene and germanene
exhibits massless Dirac fermion character from the linear crossing of p and p⁄ bands at the Fermi level
showing semi-metallic character in LB structure (DFT-LDA method). Whereas in PL germanene struc-
ture, p and p⁄ bands cross above the Fermi level at point K and K0 because of the lowering of s-like
conduction band into Fermi level. This induces the metallic character in PL Ge [485,487].
Researchers developed a tight-binding (TB) Hamiltonian model which accounts the LB structure of
Si monolayer into account [488]. According to their findings, LB silicene structure closely resembles
the monoatomic Si(1 1 1) sheet. The TB Hamiltonian study also stresses on the retention of the
Dirac point in the puckered silicene in support to an initio results. However, theoretical studies using
Fig. 24. (a) Charge density isosurfaces for r- and p-bonding in planer and low-buckled (puckered) honeycomb structure.
Yellow depicts least charge density and dark red means highest charge density. (b) Vibration frequencies of phonon modes X
versus k of Si and Ge monolayer. Reproduced with permission from Ref. [486]. Copyright 2009 American Physical Society.
different DFT package and models predict Fermi velocities with a difference of 1–2 order of magnitude
(Table 3). Weak p bonding has been held responsible for lower Fermi velocities in LB silicene because
of the hybridization lobes of neighboring atoms point in the opposite direction [488].
Further investigation into the orbital hybridization in a 2D monolayer of group IV elements was
performed using the DFT plane-wave pseudopotential method implemented in the ABINIT package
[489]. 3D crystal of C, Si and Ge has a hexagonal lonsdaleite structure were stretched along the c-axis
to notice the change in the chemical bonding and lattice configuration after the evolution of 2D struc-
ture. A clear sp3 ? sp2 transaction (strong p bond formation) was observed for C, which is a convinc-
ing evidence for the stability of the PL structure of graphene. Whereas Si and Ge failed to roll out this
hybridization change. Atomic angular-momentum projected density of states and electronic energy
indicate the partial hybridization of s and pz orbitals (dotted circle in Fig. 25) which result in sp3-like
Table 3
Fermi velocities of Dirac electrons in the vicinity of Dirac point.
Structure tf (m/s)
TB Hamiltonian model [488] ABINIT DFT Package with pseudopotentials DFT-LDA [485]
and a plane wave basis set [490]
Graphene 106 6.3 105 –
LB silicene 104 5.1 105 106
LB germanene – 3.8 105 106
Fig. 25. Energy bands of Group IV elements (C, Si and Ge) in 2D single layer and 3D lonsdaleite structure in stretched condition.
Reprinted from Ref. [489] with permission of Royal Society of Chemistry.
behavior (weak p bond). This sp3 like behavior stabilize the corrugated structure in Si and Ge
monolayers.
8.3.2. Functionalized silicene and germanene

Reactive nature of graphene toward oxygen and hydrogen have resulted in the formation of
graphene oxide and graphene which show distinctive electronic properties [491,492]. Similar to gra-
phene, efforts have been put to understand the reactive nature of silicene and germanene. As
mentioned earlier that chemically exfoliated Mg-doped Si nanosheets were capped by oxygen due to
the unstable Si–H bonding [199,479,481]. The unstable nature of Si–H bonding has been further sup-
ported by the estimated binding energy of 2.4 eV for single hydrogen atom reaction with LB silicene
from DFT-GGA calculation showing the hydrogen molecule dissociation incapacity of silicene
[177,199]. Despites these findings, hydrogenated and fluorinated silicene as well as adatom
chemisorption of metal species Li, Sc, Ti, V have been theoretically investigated [493–498]. DFT and
molecular dynamics (MD) study with GGA, PBE exchange correlation functional and DZP basis set
and norm-conserving pseudopotentials using SIESTA package determined that the hydrogenation
energy of silicene increase with increasing hydrogen adsorption ratio [493]. The hydrogenation energy
of 3.01 eV per hydrogen atom was determined for complete hydrogenation of silicene. Complete
hydrogenation of silicene increases the buckle height and Si-Si distance; and decrease the bond angle
toward bulk silicon. The band gap of hydrogenated silicene depends on the continuity of hydrogenated
region, therefore, the small band gap was observed in 25% hydrogenated silicene whereas 50% and
100% hydrogenated silicene showed no energy gap. As a result of this, zero band gap semiconductor
pristine silicene convert to insulator after complete hydrogenation. Molecular dynamics study reveals
that partially hydrogenated silicene nanosheets are stable up to 2000 K. In tight-binding (TB) model-
ing study, fully hydrogenated silicene exhibit the indirect band gap (2.2 eV) behavior between M and
Cw points; and Dirac points at K still exist [490]. Similar findings have also been reported [495] and
performed first principle DFT calculations using LDA (SIESTA package), hybrid functional HSE
(QUANTUM ESPRESSO package) and G0W0 approximation (ABINIT code) to understand the electronic
structure and stable conformation of silicane and germanane. Both, silicane and germanane, were able
to energetically degenerate chairlike and boatlike conformation (10 meV/atom) showing their stabil-
ity at room temperature. Furthermore, absence of any phonon mode in the imaginary frequencies in
the first Brillouin zone corresponds to the local energy minima and stable structure. Fig. 26 shows the
band gap structure obtained using LDA functional, demonstrating the energy band gap opening in
Fig. 26. Energy band gap structure of (a) chairlike silicane, (b) boatlike silicane, (c) chairlike germanane and (d) boatlike
germanane. All from LDA function in SIESTA package. Reprinted from Ref. [495] with permission of AIP Publishing LLC.
both conformation attributed to the change in the sp2 ? sp3 hybridization. Results show that silicane
can be direct and indirect band gap semiconductor depending on their conformation, while ger-
manane is a direct band gap semiconductor, independent of the conformation. Additionally chairlike
conformation has a higher band gap than boatlike conformation (Table 4). Spin-polarized DFT cal-
culation within GGA and HSE06 hybrid functions were performed on half and fully hydrogenated sil-
icene (SiH1/2 and SiH) [497]. For SiH1/2, the zigzag conformation was predicted to be the most stable
conformation having metallic character. Deformation charge density results predict the covalent and
ionic nature of Si–Si and Si–H bond, respectively. Si–Si bond length increases with increasing amounts
Table 4
Summary of band gap and magnetic behavior of functionalized silicene and germanene nanosheets as a function of structure and
functionalization element.
2D nanosheet Method Eg (eV) Type of Magnetic Ref.

band gap behavior
SiH TB model 2.2 Indirect – [494]
SiH HSE hybrid functional 4.0 (chairlike) Indirect – [495]
Many body G0W0 method 3.8 (chairlike) Indirect
HSE hybrid functional 3.3 (boatlike) Direct
Many body G0W0 method 2.9 (boatlike) Direct
GeH HSE hybrid functional 3.6 (chairlike) Direct – [495]
Many body G0W0 method 3.5 (chairlike) Direct
HSE hybrid functional 2.9 (boatlike) Direct
Many body G0W0 method 2.9 (boatlike) Direct
SiH LDA method 2.0 Indirect – [490]
GeH LDA method 1.5 Direct – [490]
SiH GGA method 2.36 (chairlike) Indirect – [497]
HSE06 hybrid functional 3.51 (chairlike) Indirect
GGA method 1.6 (boatlike) Direct
HSE06 hybrid functional 2.41 (boatlike) Direct
SiH1/2 GGA method 0.84 (chairlike) Indirect Ferromagnetic [497]
HSE06 hybrid functional 1.79 (chairlike) Direct Ferromagnetic
GGA method 0.53 (boatlike) Direct
HSE06 hybrid functional 1.14 (boatlike) Direct
One side SiH HSE06 hybrid functional 1.74 Direct Ferromagnetic [500]
PBE-GGA method 0.94 Direct Ferromagnetic
One side GeH HSE06 hybrid functional 1.32 Direct Ferromagnetic [500]
PBE-GGA method 0.41 Direct Ferromagnetic
SiH DFT-GGA 2.11 (chairlike) – – [498]
GeH 0.95 (chairlike)
SiF 0.70 (chairlike)
GeF 0.19 (chairlike)
SiH1/2 DFT-GGA 0.95 Indirect Ferromagnetic [499]
SiH DFT-GGA 2.31 (chairlike) – [496]
1.93 (boatlike)
1.96 (top)
SiLi 0.25 (chairlike)
0.55 (top)
SiF 0.98 (chairlike)
1.40 (top)
GeH 0.90 (chairlike)
1.60 (boatlike)
2.32 (top)
GeLi 0 (chairlike) Metallic
0.26 (top)
GeF 0 (chairlike) Metallic
0 (top) Metallic
Ge8V1 0.1 (hollow)
GeSc –
GeTi –
GeH Topochemical deintercalation of CaGe2 1.53 Indirect [501]
Double layer Si–H DFT-GGA 1.2 Indirect [502]
Double layer SiP 1.5 Indirect
Fig. 27. Projected density of state of one-sided semi hydrogenated (a) silicene and (b) germanene from HSE06 functional used
in Vienna an initio simulation package (VASP). Reprinted from Ref. [500] with permission of Royal Society of Chemistry
Publisher.
of hydrogen due to the saturation of pz orbitals of Si by H atoms which does not allow the p bond for-
mation. Whereas chairlike and boatlike SiH and SiH1/2 are semiconductor. The interesting finding of
this study is the ferromagnetic property of SiH1/2 in chairlike conformation because of the delocalized
p electrons which form long-range exchange coupling [497,499]. Despite the non-magnetic nature of
silicene, non H bonded Si atoms contribute 85% of magnetic movement and only 3% come from H
bonding Si atoms [497]. These findings matches well with the first principal calculation results in
one-side hydrogenated silicene and germanene [500]. Both silicene and germanene develop ferromag-
netic behavior after one-sided partial hydrogenation as clearly visible from Fig. 27.
Another study on chairlike-configuration of hydrogenated and fluorinated silicene and germanene
from DFT using GGA and PWA method in VASP reveal that fluorinated structure is energetically favor-
able to synthesize experimentally because the estimated energy of formation is highly negative com-
pared to hydrogenated sheets [498]. Recently, adsorption of metal atoms has also been attempted to
obtain the electronic functionalization of silicene and germanene from DFT in SIESTA package using
GGA for the exchange–correlation functional [496]. Metal atoms Sc, Ti and V atoms were added at
the center of the hexagonal rings. Addition of atoms having planar 3d-orbital C4 symmetry does not
obey the C6 hexagonal symmetry resulting the sublattice symmetry breakdown. Despite this, planer
orbitals of adatom and monolayer show the strong sign of hybridization at the Fermi level. As a result
of hybridization, flat band were observed in Fermi energy for all adatoms (Sc, Ti and V), but Ge8V1 hol-
low structure demonstrates the linear dispersion at K/K0 at points in valence region thus retain the
Dirac cone. This is explained by minimal hybridization between the 3dz2 (adatom) and valence pz
(monolayer) orbitals. This feature avoids very important for adaption of silicon and germanene in
device application as adatoms surface state. Evidence of free standing GeH nanosheets obtained from
topochemical deintercalation of GeH2 crystal has been reported [501]. The GeH is an indirect band gap
semiconductor, thermally stable up to 75 °C and takes 5 months to oxidize. This study has kept the
expectation alive the use of Ge and Si monolayers in electronics and spin-electronic devices and sen-
sors in the near future. First principle an initio study of effect of dangling bonds on the double layer
Silicene (DL-Si) have carried out by saturating dangling bonds with hydrogen and substitutional dop-
ing of phosphorus [502]. This double layer was obtained from cooling liquid Si confined in a slit nano-
pore from MD calculations [503]. Out of plane Si–Si bond has a higher bond length of 2.47 Å than in
plane bond length (2.32 Å) because of the three-coordinated Si atoms in DL-Si [502]. Therefore, only
one dangling bond per Si atom. Band structure simulated at T = 0 K shows the metallic character of DL-
Si and indirect band gap semiconductor nature of DL-SiH and DL-SiP structure (1.2 and 1.5 eV, respec-
tively). These sheets can be converted into p-type semiconductor by controlling hydrogenation (80%)
or substitution of phosphorous (50%). Interstitial doping of Na in DL-Si–H and partial replacement of
P to S (act as electron donor) could result in n-type semiconductor. As mentioned above in the case of
double layer Si, further stacking of monolayers change the bonding within Si atoms, so the electronic
and density of state [504]. For n P 3 monolayers combination, sandwiched layers unable to form the
p-chain due to the tetrahedral bonding.
8.3.3. Strain induced effect in Si and Ge monolayer and their functionalized derivative
Electronic structure of monolayers can also be tailored under the influence of external mechanical
stress without the need of doping. Electronic properties of graphene were studied under uniaxial and
isotropic strain using first principle calculations [505]. Graphene does not show any change in its
semi-metallic zero band gap under uniaxial strain of 30%, but opens a small energy gap at narrow
strain range. The study also reports the change in perpendicular and parallel component of Fermi
velocity. Influenced by these findings, researchers have undertaken the study of strain effect on other
2D materials such as silicene [506–509], germanene [507,510], silicane [506,511], MoS2 [512] etc.
Typical silicene which has semi-metallic character similar to graphene, convert to metal when the ten-
sile and compressive strain >7.5% is applied in-plane during an initio calculation [508]. This semi-
metal to metal transaction is attributed to the downward movement of the lowest conduction band
at C-point. It has been performed a DFT calculations on the stability of germanene under tensile strain
using fully relativistic Rappe–Rabe–Kaxiras–Joannopoulos normconserving pseudopotentials and LDA
[510]. Germanene lattice is stable up to 16% biaxial tensile strain. Simultaneously, Dirac cone shifts
toward higher energy and hole-doped is achieved. They also observed the shift in the phonon frequen-
cies at 427–363 cm1 (G mode) and 366–287 cm1 (D mode) at 5% biaxial strain. Biaxial strained sil-
icene also found to be stable up to the application of 17% strain [509]. Silicene remain semi-metallic
until 5% strain as it Dirac cones stay at Fermi level, but gradually converts to hole-doped Dirac states. G
and D mode phonon frequencies of silicene also affect from strain similar to germanene. Si and Ge
monolayer not only transform from gap less semi-metallic to p-type semiconductor under tensile
strain, but also exhibit n-type transformation while the compressive strain is applied [507]. Dirac
point move upward above the Fermi level of tensile strain thus behaves as p-type semiconductor
(Fig. 28c). In case of compressive strain, Dirac point move downward below the Fermi level and
become n-type semiconductor (Fig. 28b). The Dirac point remain at the Fermi level at 0% strain
(Fig. 28a). Measured charge carrier accumulated near the Dirac point of Si and Ge monolayer is sum-
marized in Table 5. First principle DFT-LDA calculation performed on hydrogenated silicene also exhi-
bit the indirect to direct bandgap transaction at 2.74% tensile strain; and semiconductor to metallic
at.% strain as conduction band minimum and valence band maximum coincide at C-point [511].
They also reported the red shift in the optical absorption edge of strained silicane, which falls into
the visible range. It is evident from the above mentioned findings that semiconductor behavior can
Fig. 28. Band structure of silicene at strain (a) e = 0%, (b) e = 5% (compressive) and (c) e = 5% (tensile). Fermi level are shown at
the line at E = 0 eV. Reprinted from Ref. [507] with permission of Elsevier Publishers.
Table 5
Charge carrier accumulated near the Dirac point of strained Si and Ge monolayer [507].
2D structure Strain (e) ED EF (eV) b (eV Å) Charge carrier (cm2) Semiconductor type
Silicene 0.08 0.127 3.52 4.2 1012 n-type
0.10 0.073 3.15 1.7 1012 p-type
Germanene 0.05 0.181 3.49 8.0 1012 n-type
0.05 0.050 3.25 0.7 1012 p-type
be induced or band gap can be easily manipulated in semi-metallic 2D monolayers by strain and
expensive elemental doping route could be scrapped in electronic and optoelectronic devices.
Monolayers of Si and Ge have been studied theoretically long before the exfoliation of single layer
graphene because of their widespread use in the semiconductor industry. However, graphene has won
the race, as a single monolayer of graphene is stable in air for a long time whereas, silicene and ger-
manene monolayers are not stable under ambient conditions. However, a recent study published in
2014 authors have achieved up to 24 h stability in air for silicene [513]. Additionally, silicene has a
low bucked structure compared to the hexagonal structure of graphene, which also contribute to
the stability of the 2D material of Si and carbon. In the light of the above evidence, silicene has mainly
been studied theoretically and has not been utilized in the device fabrication. However, in long term,
silicene and germanene have the potential to replace conventional Si based substrate technology and
contribute toward the miniaturization and enhanced performance of electronic devices.
8.4. 2D layered oxide and hydroxide
As discussed earlier in this article, exfoliation of layered compounds has attracted enormous atten-
tion and exposed novel properties due to the lateral quantum confinement effect. Similarly, successful
exfoliation of layered oxides of transaction and rare earth metals and hydroxides have also been
achieved, which has widened the scope of nanosheets in conventional and futuristic applications.
Because of exceptionally rich structural diversity and electronic structure, these oxides and hydroxide
nanosheets have found applications in catalysis, optical, electronic and spin-electronic devices
[172,514]. This section presents the advancement in the synthesis and modulation of fundamental
properties of oxide and hydroxides nanosheets.
8.4.1. Synthesis
Oxides and hydroxide nanosheets are usually delaminated by chemical exfoliation using bulky
guest ions or organic molecules as intercalation agent. As a result of intercalation, high degree of swel-
ling and weak inter-layers interaction is achieved. The chemical exfoliation process is highly depen-
dent on intrinsic as well as extrinsic factors. Intrinsic factors include the chemical composition of
layers, ions present between the layers (normally alkali metal ions) and electrostatic forces that held
the individual layers together. Whereas the dielectric constant, polarity and surface tension are extrin-
sic factors. Optimization of these factors results in the highest degree of swelling followed by small
mechanical action, such as sonication or stirring leads to the complete exfoliation of layered com-
pounds into single and few layer nanosheets. Quaternary ammonium cations, propylammonium
cations, tetrabutylammonium (TBA) cations etc. [515,516] are mainly used for layered oxides and for-
mamide, butanol, N-Vinyl-Pyrrolidinone (NVP) etc. [514] are used for hydroxides. Both polycationic
and polyanionic nanosheets are derived from the chemical exfoliation process depending on the
chemistry of layers and ions present between the layers [514,517–519].
Metal oxide crystal layers are constituted from a corner or edge shared MO6 metal octahedral units
(M = Ti, Mn, Ta, W, Nb) and alkali cations (K+, Cs+, Rb+) are present in the layers galleries and provide
the opportunity for cation-exchange to exfoliate nanosheets. These alkali cations also maintain the
charge neutrality of the crystal at room temperature. Several metal oxide such as perovskite type oxi-
des La0.90Eu0.05Nb2O7 [142], K1.5Eu0.5Ta3O10 [143], KLnNb2O7, K2Ln2Ti3O10, and RbLnTa2O7 (Ln:
Lanthanide Ion) [144], KCa2Nb3O10 [145,146], Cs0.7Ti1.825O4 [520,521], K0.45MnO2 [522,523], RbTaO3
[524] and Cs6+xW11O36 [525] etc. have been exfoliated into nanosheets. In general, bulk crystals are
prepared by calcination at high temperature (800–1300 °C) followed by acid treatment to produce
protonated form [514]. In the next step, protons are replaced by bulkier foreign cations, which lead
to a substantial increase in the volume which was followed by mechanical shearing to break the loose
aggregate of nanosheets. However, due to the non-uniform size of the parent bulk crystal produced by
solid state calcination, nanosheets of the lateral size of hundreds of nanometer to few microns are
obtained which limit the use in the fabrication of electronic devices [172,514]. To overcome this issue,
single crystal of K0.8Ti1.73Li0.27O4 [514,517] and K4Nb6O17 [514,526] of size up to few mm have been
synthesized by melting and recrystallization method. These single crystals were further utilized to
delaminate nanosheets by chemical exfoliation process. Nerve the less, bottom-up approach such as
epitaxial growth of titanium oxide nanosheets by electron beam evaporation on Pt(1 1 0) substrate
[527], chemical oxidation of Mn2+ in aqueous solution of tetramethylammonium (TMA) [514,528]
have also been developed to synthesize oxide nanosheets. Another bottom-up approach involves
the chemical reaction between organic titanium precursor, titanium tetraisopropoxide (TIP) and
tetramethylammonium (TMA) hydroxide in aqueous solution under refluxing conditions [514,529].
In contrast to the large family of layered oxides, limited positive charged hydroxide layered system
have been practically witnessed. Hydrotalcite-like layered double hydroxide (LDH) shows the anion
exchangeability. The general formula of LDH is represented as M2+ 3+
1xM x(OH)2A
n
x/nm H2O where
M are Ni , Co , Mg , Zn etc. and M are Co , Al , Fe etc. [514,518]. These M2+ and M3+ metal
2+ 2+ 2+ 2+ 2+ 3+ 3+ 3+ +
ions forms octahedral-brucite-like M(OH)2 layers and An anions between the interlayers. Unlike the
metal oxides, precursor crystals of hydroxides are synthesized by the reaction of metal salts in alkali
solution by co-precipitation method [514–516]. Successful efforts have been made to decrease the elec-
trostatic interaction of layers during the co-precipitation of the parent crystal by replacing alkali anions
by surfactants e.g. sodium dodecyl sulfate [515,516]. Literature also reports the exfoliation of LDH in
organic solvents such as formamide by the intercalation of amino acids and NO 3 at room temperature
eliminating the use of expensive organophilic anions [530]. Moreover, synthetic approach for homoge-
neous precipitation of LDH in carbonated form are being developed by the hydrolysis of M2+ metal
halides (M = Mg, Ni, Co, Fe, Zn) and aluminum chloride in the presence of urea and hexamethylenete-
tramine (HMT) [514,531,532]. LDH crystals were treated with acid-salt exchange to remove carbonate
anions followed by sequential exfoliation in formamide solution. However, the need of amphoteric nat-
ure of Al3+ for hydroxide crystal precipitation has prevented the researcher to produce complete transac-
tion metal LDH system [514]. Researchers have been able to overcome this problem by newly developed
topochemical oxidative intercalation method [514,533,534]. The overall process is a combination of
homogeneous precipitation of brucite-like hydroxide via hydrolysis and selective oxidation of transac-
tion metal divalent ions into trivalent metal ions by weak halogens (Br, I) in acetonitrile or chloroform
organic solvent. So far, Ni2+–Co3+, Co2+–Co3+ and Co2+–Fe3+ LDH nanosheets have been prepared by this
route.
Unique properties of rare earth elements have also ignited the quest to develop layered rare earth
hydroxides nanosheets ([RE3+(OH)2.5xH2O]0.5+ where RE = Eu, Gd, Sm, Y, Er, Nd, Lu, Dy, Ho) and are
recent addition to the 2D family [514,535–537]. Presence of charge balancing ions (Cl, NO 3 etc.)
allow the scientists to exfoliate nanosheets via anion-exchange method as discussed in Section 5.2
for Eu hydroxide. Exfoliation of Gd hydroxide has also been reported in the literature with oleate ions
as intercalating agent [519]. As mentioned earlier, despite the suitability for bulk production of
nanosheets, chemical exfoliation creates defects in nanosheets and colloidal solution become unstable
over time. Therefore, successful attempts have been made to exfoliate nanosheets on water, an
environment friendly solvent. Incorporation of lactate or carboxylate anion between inter lamellar
galleries of Mg2+–Al3+ system (Mg/Al = 3) modulates the chemistry, thus LDH crystals swell and exfoli-
ated in water [514,538]. However, long exfoliation time (1–2 weeks) is needed to obtain the colloidal
solution.
8.4.2. Assembly of 2D nanosheets

Oxide and hydroxide nanosheets carries negative and positive charge, which allows them to dis-
perse in the colloidal solution. Additionally, high aspect ratio due to their sub nanometer thickness
and large lateral size finds these nanosheets as a suitable source as building block for nano structural
films in nano-architecture devices. These features allow the easy fabrication of nano structured films
by restacking nanosheets into the desired structure. Thin films of up to 10 nm and hollow nanometer
thick shells have been obtained from freeze drying [539] and spray drying [540] of exfoliated titanium
oxide nanosheets dispersed in colloidal solution, respectively. However, it is difficult to obtain the
requisite architecture and synthesize the composite nanofilms from above said methods. On the other
hand, oxide and hydroxide nanosheets can be laid on the substrate due to their flat morphology and
charge. Several wet-process synthesis such as spin coating [541], drop casting [542], dip coating [543],
flocculation [544,545], electrophoretic deposition [546,547] and layer-by-layer (LBL) self-assembly
[548] have been utilized on nanosheets alone or combining oxide and hydroxide nanosheets with
polyions having a thickness from 3–4 nm to 100 nm. Although, device performance relies on the
thickness and continuity as the electronic properties modulates with increasing thickness. Film
formed by conventional wet-processes such as spin-coating, drop casting, dip coating, electrophoretic
deposition and so on lack in continuity (Icelandic structure) and thickness control and contains poros-
ity. On the other hand, flocculation and LBL self-assembly technique have found to be suitable for pre-
cise control of thickness at nanometer scale. Careful assembly of 2D nanosheets with/out organic
molecules results in the exciting functionalities due to the coupled interaction at the nanosheets inter-
face [514].
In principle, LBL self-assembly technique utilize the electrostatic attraction between the
nanosheets and/or polyions to fabricate nanofilms with precise thickness and large surface area cover-
age. Electrostatic sequential deposition and Langmuir–Blodgett (LB) deposition are two commonly
used techniques for nanofilm synthesis for application in magneto-optical (MO), electronic,
photocatalysis etc. to develop functional properties.
Electrostatic sequential deposition technique, also known as molecular beaker epitaxy, has a long
history in pharmaceutical and virology research where proteins, virosomes, antigens, etc. are depos-
ited on a wide variety of particles for the delivery [549,550]. With the evolution of a 2D class of materi-
als having a large lateral surface, this technique has been adopted due to its ease, simplicity and cost
effective nature. In this method, atomically flat substrate (Si/SiO2, indium tin oxide (ITO), SrRuO3,
SrTiO3 etc.) is first dipped in an aqueous solution of polyelectrolyte followed by a colloidal solution
of oppositely charge bearing nanosheets. This process is repeated several times until the desired
thickness is achieved. Careful selection of polyelectrolytes is necessary based on the nature of
charge on nanosheets and the chemical compatibility with nanosheets. Polyethylenimine (PEI),
poly(diallyldimethylammonium chloride) (PDDA), aluminum polyoxocations [AlO4Al12(OH)24(H2O)12]7+
or popularly known as Al13 Keggin ions are commonly used for nano-architectural film fabrication
with oxide nanosheets, whereas polystyrene sulfonate (PSS), poly(acrylic acid sodium salt),
poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(vinyl sulfate) potassium salt are used with
hydroxide nanosheets [514,544,545,551–553].
Unlike the electrostatic sequential deposition, LB deposition of film requires skilled personal, as the
quality of the deposited film is governed by several factors such as temperature, surface tension, com-
pression force, immersion and withdraw rate of substrate from solution. In the typical LB deposition
process, a monolayer of nanosheets is formed on the liquid surface by the careful maneuver of LB
trough arms. Uniform dispersion of nanosheets in water usually achieved using surfactants
[514,554–557]. Movement of LB trough arms create sufficient/optimum compression to make dense
monolayer. If the compression pressure is low, nanosheets will be loosely packed and thus porosities
will be visible when examine under an electron microscope and AFM. On the other hand, high com-
pression pressure leads to the formation of overlapped patches, which result in the breakdown of
the film texture. Change in the nanosheet solution temperature in LB trough also changes the surface
tension of the liquid and thus optimum compression pressure. Once the dense monolayer on liquid
surface is obtained, substrate is immersed in the liquid solution and lifted at constant velocity to
deposit the monolayer of nanosheets. This process is repeated several times for the sequential growth
of nanostructured film. Schematic illustration of the LB deposition process is presented in Fig. 29.
Nanostructured films obtained from both, electrostatic sequential deposition and LB deposition
process, demonstrate good interlayer registry (Fig. 30b) [558–560]. This well-defined registry devel-
ops novel properties in the nanostructured film [558]. Uniform enhancement of absorption intensity
in the UV–vis absorption spectrum provides the concrete evidence of sequential growth of nanostruc-
tured films by LBL self-assembly technique [558,561,562]. Low angle XRD, HRTEM and EELS spectra
Fig. 29. Schematic illustration of nanosheets transfer on flat surface by Langmuir–Blodgett deposition process. Reprinted from
Ref. [146] with permission of ACS Publisher.
Fig. 30. (a) Atomic model of Ca2Nb3O10 nanosheet showing A and B-sites substituted with Sr2+ and Ta5+, respectively. (b) Cross
sectional HRTEM micrograph of multilayer assembly of Ca2Nb3O10 film showing well defined interlayer registry. (c) Dielectric
constant as a function of film thickness and (b) leakage current density vs. applied voltage curve of A and B-site modified
various Ca2Nb3O10 films. Reprinted from Ref. [559] with permission of John Wiley and Sons Publisher.
across the film are further utilized to confirm the periodic nanostructure of nanosheets arrangement,
their thickness and chemical composition [514,559,560].
Another easy and versatile technique which leads to the restacking of oxide and hydroxide
nanosheets into the colloidal solution is flocculation. This method is commonly used in remote regions
of developing country to purify water by adding potassium aluminum sulfate [KAl(SO4)212(H2O)].
From the 2D materials point of view, electrolyte containing opposite charge to the nanosheets is
added. The Electrostatic attraction between electrolyte and nanosheets result in the restacking of
nanosheets in irregular fashion. Compared to the LBL self-assembly method, due to the irregular
restacking of nanosheets, well-defined interlayer registry not observed in the flocculated nanocom-
posites [514,563,564]. Other features of flocculated nanocomposites are their porous nature,
micro/nano texture and high surface area where forging molecules can be incorporated to develop
functionalities which have potential applications in sensors, electrodes and controlled drug delivery
and so on. Therefore, nanostructured multilayer composite films and nanocomposites can be prepared
on a variety of flat and curved substrates as well as in solution which possess novel functionalities for
a multitude of applications and open new horizons for use of oxide and hydroxide nanosheets in exist-
ing and future technologies.
8.4.3. Electronic properties and application in electronic devices

High electronic transport property of graphene has attracted wide attention of electronic industry;
oxide and hydroxide nanosheets have also proved their importance as an electrical insulator or wide-
band gap semiconductor or high-j dielectric for energy storage, capacitors, random access memories,
gate insulator etc. [565]. However, most of the oxide nanosheets synthesized so far do not show super-
ior electronic transport properties due to the empty d orbitals. However, in nanosheets, d0 orbital of
metals and filled p orbitals of ligands develop functionalities such as insulator and wide band gap
semiconductor [172,566]. Therefore, to investigate the novel functional properties of oxide and
hydroxide nanosheets and interfacial effect, these nanosheets have been assembled in different
combinations of polyelectrolyte, oxide and hydroxide.
Nb3O8 film prepared by sequential deposition of nanosheets generates anodic photocurrent when
the film is illuminated with 270 nm UV light and show a photon-to-electron efficiency of 1.8% [562].
UV irradiation analysis and cyclic voltammetry results also suggest the indirect, wide band gap of
3.58 eV and flat band potential of 1.32 V vs. Ag/Ag+ respectively, which is close to 3.84 eV and
1.27 V vs Ag/Ag+, values observed in the case of Ti0.91O2 nanosheet. Despite this, reduction/oxidation
ratio of the electroactive Nb atom was only 6.3% compared to 50%, suggesting the highly electroac-
tive nature of Ti0.91O2 nanosheet than Nb3O8 [561,562].
Recently, Dion–Jacobson phase type perovskite oxide nanosheets of LaNb2O7 and Ca2Nb3O10 were
deposited using the LB deposition method on SrRuO3 substrate to artificially engineer the interface
and create super lattice [558]. Super lattice is usually observed in the bulk materials, however, super
lattice have been created in the nanostructured films by sequential deposition of nanosheets.
Piezoelectric force microscopy (PFM) measurement of different super lattice (Fig. 31a) exhibit the
ferroelectric behavior as the large area hysteresis has been observed in (LaNb2O7/Ca2Nb3O10)5 super
lattice film. On the other hand, multilayer layer film of LaNb2O7 and Ca2Nb3O10 does not form hystere-
sis during PFM measurement thus showing paraelectric behavior (Fig. 31b). It can be clearly under-
stood from PFM results that paraelectric to ferroelectric transformation occur due to the super
lattice formation and increased number of heterointerfaces modulates the PFM response (Fig. 31e).
It can be inferred from the reduced leakage current in case of (LaNb2O7/Ca2Nb3O10)5 super lattice film
(Fig. 31c) that ferroelectric behavior is an intrinsic property of the super lattice film attributed to inter-
facial effect. Low leakage current is certainly required for the future evolution of electronic industry
with the downsizing of gate length. Sharp interface between substrate and nanosheet also suggest
the absence of dead layers due to the negligible strain and interdiffusion. The super lattice structure
also enhances the dielectric constant (er = 110) compared to the theoretically estimated value of
er = 89 from parallel capacitor model (Fig. 31d). Underestimation of er is correlated to the residual
dipoles at the heterointerfaces which increase the polarization of super lattice structure.
Furthermore, dielectric constant and leakage current characteristics of oxide nanosheets have also
been tailored by modifying the A and B-sites of nanosheets (Fig. 30a) [559,560]. A and B-sites of per-
ovskite type Ca2Nb3O10 nanosheets were modified by lattice substituting with Sr2+ and Ta5+ ions,
respectively [559]. It is evident from Fig. 30c that the dielectric constant of oxide nanosheets enhance
with the A-site modified with Sr2+ ions by 30 irrespective of thickness of film. Sr2Nb3O10 nanosheets
has the dielectric constant of 240 whereas dielectric constant value decrease with B-site modification.
B-site modified film of 7.5 nm thickness shows the leakage current density of 108 A/cm2 due to the
higher electronegativity of Ta5+ compared to Nb5+ which leads to a larger band gap which is lower
than the International Technology Roadmap for Semiconductors (ITRS) (Fig. 30d) [559,565].
Therefore, substitution of A-sites improves the insulating properties, whereas B-site modification pro-
vides superior leakage current characteristic and reduces permittivity. Similarly, A-sites of La0.95Nb2O7
nanosheet modified with Eu3+ reduce the dielectric constant, leakage current density and permittivity
of nanostructured film prepared by the LB deposition method [560].
Cyclic voltammetry analysis of hetero-nanostructure film of Ti0.91O2 and redox MnO2 nanosheets
shows oxidation and reduction of Mn3+ and Mn4+ at .15 and 05.2 V respectively, which is ascribed
to the movement of Li+ ions in the interlayer galleries of MnO2 nanosheets [567]. Reduction of
Fig. 31. Amplitude vs. applied voltage curve of (a) different superlattices and (b) multilayer films as a response of PFM
measurement with the corresponding stacked structures. (c) Leakage current density vs. applied voltage and (d) dielectric
constant vs. frequency distribution of superlattice structure and multilayer film. (e) Graphical representation of dependence of
piezoresponse amplitude (at +1 V) on number of heterointerface. Reprinted from Ref. [558] with permission of ACS Publishers.
MnO2 sheets occurs due to the generation of photoelectron from Ti0.91O2 nanosheets, which again oxi-
dize from electrochemical methods. The electrochemical behavior of the hetero-nanostructure film
also varies with the interlayer environment, highlighting the importance of deposition sequence dur-
ing the deposition process.
8.4.4. Catalytic and luminescent properties

Oxide and hydroxide nanosheets have also studied for catalytic and luminescent properties.
Intra 4f-transaction of lanthanide ions results in the well-defined emission from oxide phosphors
has gained attention of the scientific community. Researchers have studied the luminescent property
of A-site substituted three different layered perovskites, K2Ln2Ti3O10 (Ln: La, Pr, Sm, Nd, Eu, Gd, Tb,
Dy), KLnNb2O7 (Ln: La), and RbLnTa2O7 (Ln: La, Gd) [144]. A-site of layered oxides having Ln3+ ions
Fig. 32. Photoluminescence spectrum of (a) Gd1.4Eu0.6Ti3O

10 (red) and (b) La0.7Tb0.3Ta2O7 (green) nanosheet solution [144]. (c)
Excitation and emission spectra of LBL self-assembled film prepared from (a) exfoliated solution (b) 0.1 M NaOH and (c) 0.1 M
HCl Bi2SrTa2O9 nanosheet solution. Reprinted from Ref. [548] with permission of ACS Publisher.
were substituted with Eu3+ and Tb3+ ions for red and green emission, respectively. Fig. 32a and b
shows the photoluminescence spectrum of Gd1.4Eu0.6Ti3O
10 and La0.7Tb0.3Ta2O7 nanosheets colloidal
solution. It is clearly visible from the Fig. 32a and b that Gd1.4Eu0.6Ti3O10 and La0.7Tb0.3Ta2O

7 emits
strong red and green emission when excited with 254 nm wavelength which has higher energy than
their respective band gap. These visible emissions occur due to the energy transfer within the
nanosheets. Two step energy from Ti–O ? Gd3+ and Gd3+ ? Eu3+ within the nanosheets has been
attributed to the strong red emission intensity. They have also demonstrated that the emission inten-
sity can be modified by changing the orientation of nanosheets using magnetic fields. Ida and cowork-
ers have also observed blue visible emission form exfoliated Bi2SrTa2O9 nanosheets [548]. Higher
intensity from nanosheets in 0.1 M NaOH solution than nanosheets in 0.1 M HCl solution illustrates
the strong reliance of the surface environment on emission intensity (Fig. 32c).
Nanosheets of Eu3+ activated (K1.5Eu0.5)Ta3O10 oxide phosphor has exhibited photoluminescent
property in the far-red region in host and direct photoactivator excitation mode [143]. Several peaks
were observed in the emission spectra attributed to the 5D0–5FJ transaction of Eu3+ upon excitation
with wavelength of 322 nm on dried film. This illustrates the suitability of tantalite oxide as host
for Eu3+ activated phosphors for UV to far-red energy conversion. Similar findings have been observed
for Eu0.56Ta2O7 nanosheets showing 18 times higher emission intensity by host excitation compared to
the direct Eu3+ excitation [568]. Researches have also reported the dimensionality effects on the pho-
toluminescent behavior of exfoliated Eu3+-doped La0.90Eu0.05Nb2O7 nanosheets and parent bulk crystal
K1xHxLa0.90Eu0.05Nb2O7 [149]. Contrary to nanosheets where host excitation emits a higher intensity
than direct photoactivator excitation, in bulk crystal direct excitation yields more intense emission
than the host excitation. This behavior has been correlated with dimensionality of the host structure
and confinement of the energy-transfer process between the host layer units and Eu3+ activators [149].
A part of the luminescence property, Ca2Nb3O 10 nanosheets have also utilized as a catalyst for
generating hydrogen [563,569]. Researchers have incorporated Rh(OH)3 into the galleries of
Ca2Nb3O
10 by flocculation [563]. Calcination of Rh(OH)3–Ca2Nb3O10 complex at 350 °C convert
Rh(OH)3 into Rh2O3 and form Nb–O–Rh covalent bond. The results of the hydrogen evolution experi-
ment from methanol show the superior catalytic activity of Rh2O3 over Rh(OH)3. Moreover, Rh2O3–
Ca2Nb3O 10 system generate 40% more hydrogen compared to the well-known Pt–Ca2Nb3O10 system

for an equivalent amount of catalytic metal. In another study, Ca2Nb3O 10 nanosheets have shown to
produce hydrogen from water splitting however the quantum efficiency is only 0.22% [569]. The quan-
tum efficiency of these nanosheets significantly enhance to 7.5% by incorporating Pt nanoparticles on
nanosheets. These examples illustrate the catalytic property of oxide nanosheets, which can be
improved by altering the chemistry of the host nanosheets which is an open area of research and rela-
tively unexplored.
8.4.5. Magnetic properties and application in spin-electronic devices

A part of the insulating property of oxide nanosheets, ferromagnetic properties of oxide and
hydroxide nanosheets have also attracted wide attention of the scientific community. The
ferrimagnetic property of Fe3O4 nanoparticles has acted as a motivation to analyzing magnetic proper-
ties of iron oxide and other transaction metal oxide/hydroxide nanosheets. Moreover, the quest of
room temperature ferromagnetic semiconductors for spin-electronic devices have also helped to
evolve this field [172,570,571]. Therefore, several doped and co-doped TiO2 nanosheets such as
Ti0.8Co0.2O2 [571–574], Ti0.6Fe0.4O2 and Ti0.75Fe0.1Co0.15O2 [575], Ti0.8Co0.2O2/Ti0.6Fe0.4O2 [575],
Ti(5.2 2x)/6Mnx/2O2 (x = 0.0–0.4) [575], sodium/potassium iron oxide [576] etc. have been studied
and reported ferromagnetic at room temperature. Nanosheets exhibits highly anisotropic magnetiza-
tion as measured in the field parallel and perpendicular to the film. For Ti0.8Co0.2O2 nanosheets, the
maximum magnetic moment was the 1.4 lB/Co in field parallel to the film, which was 1.5 times
higher compared to perpendicular direction along with spin moment of 1 lB/Co for the low-spin
(S = 1/2) state of Co2+ which stabilize the ferromagnetic ordering [572]. This anisotropic nature of
magnetization has been attributed to the 2D nature of nanosheets. An absorption edge near to 4 eV
in magnetic circular dichroism (MCD) spectroscopy suggest strong spin polarization in the
Ti0.8Co0.2O2 nanosheets [572–574]. For potential application in spin-electronic devices, literature have
also stressed on the interlayer coupling during super lattice formation to tailor the magneto-optical
response. Magneto-optical response enhances by one order in case of (Ti0.8Co0.2O2/Ti0.6Fe0.4O2)5
(105 deg/cm) in comparison to (Ti0.8Co0.2O2)5(Ti0.6Fe0.4O2)5, (Ti0.8Co0.2O2)10 and (Ti0.6Fe0.4O2)10
(104 deg/cm, absorption edge 280 nm) [572–575] (Fig. 33). Similar ferromagnetic and
magneto-optical responses have been reported for Fe/Co co-doped Ti0.75Fe0.1Co0.15O2 nanosheets at
400–750 nm [575]. This enhancement in the Faraday response is credited to the d–d transaction
(Co2+–Fe3+) from first principle calculations. Moreover, hydroxide nanosheets of Co–Al have also
shown magneto-optical properties, however their magneto-optical response is lower than the oxide
Fig. 33. Optical absorption and MCD spectra of nanosheet superlattice in various sequence. (a and b) (Ti0.8Co0.2O2)10 and
(Ti0.6Fe0.4O2)10, (c and d) (Ti0.8Co0.2O2)5(Ti0.6Fe0.4O2)5 and (e and f) (Ti0.8Co0.2O2/Ti0.6Fe0.4O2)5. Reprinted from Ref. [573] with
permission of American Association for the Advancement of Science Publisher.
nanosheets [577]. These findings indicates the importance of band engineering to maximize the mag-
neto-optical response in the blue light region to future applications.
8.5. Graphene analogue binary compound of group IV and III–V elements
Due to the unusual electronic and quantum transport properties of Si and Ge single layers,
researchers have also shown interest in honeycombed binary compounds of group IV elements and
III–V compounds [486,578–587]. Most of these binary compounds have been studied theoretically
and their synthesis remains a challenge for researchers as they belong to the family of tetrahedrally
coordinated semiconductors in 3D. Researchers have undertaken a comprehensive theoretical study
using first principle plane-wave calculations within the framework of DFT to determine the existence
of monolayer honeycomb structures as a local minimum on the Born–Oppenheimer surface [486].
Most of the compounds (22 out of 26) were found to be stable in honeycomb hexagonal structure
either in finite (flakes) or infinite length. Compounds containing the first row of elements (B, C and
N) exhibit stable planar honeycomb (PL) structure (SiC, GeC, SnC, AlN, GaN, InN, BP, BAs and BSb) simi-
lar to graphene and BN, whereas other stable compounds (SnGe, SiGe, SnSi, InP, InAs, InSb, GaAs, GaP
and AlSb) have low buckled honeycomb (LB) structure similar to silience and germanene. Stability of
structures is attributed to their positive X (k) in the Brillouin zone. It is also observed that the increas-
ing length in low buckled structure results in weak p–p bonding, thus sp2 orbitals slightly dehybri-
dized and form sp3 like hybrid orbitals. This study also projects these binary compounds as a
semiconductor. Band gap, in-plane stiffness, and Poisson’s ratio of binary compounds significantly
depend on constituent atoms.
Another detailed study on zinc blend structure compounds of group III–V, II–VI and IIB–VI from
DFT calculations using the projector augmented wave method in the plane-wave code VASP with
GGA approximation with Perdew–Burke–Ernzerhof (PBE) parametrization. Each binary compound
was tested for three structures in stability analysis: planar honeycomb (P-6M2), buckled honeycomb
(PMN21) and tetragonal structure (P4/NMN). It is interesting to note that some binary compounds
coexist in two phases (BN, AlN, AlP). Buckling distance, energy of compound formation (Eform), elec-
tronic band structure, quantitative value of indirect and direct band gap semiconductor values shows
good correlation with previous study [486]. Change in the above mentioned property is attributed to
the atomic radius and electronegativity of constituting atoms of the compound. Fig. 34 present the
summary of results of binary compounds of group III–V, II–VI and IIB–VI.
The band structure, nature of the band gap (direct or indirect), theoretical lattice parameters, bulk
modulus and cohesive energy of nitride, arsenide and phosphides of group III have been estimated
from first principle calculation using different approximations [580–582]. Generalized gradient
approximation (GGA), Engel and Vosko proposed GGA (GGA-EV); and local-density approximation
(LDA) were used for exchange correlation potential in the calculations. The results are comparable
with the other findings.
Theoretical studies also demonstrate that direct–indirect band gap transaction can be induced in
the group IV carbides by strain engineering [579]. Changing the bond length results in the overlapping
of electronic band gap with other zinc blend type 2D binary compounds. This has potential application
in photocatalyst, water splitting and nanoelectronic [578,579]. Electronic and magnetic properties of
group VI and III–V binary compounds can be modulated by controlling adsorption of hydrogen or fluo-
rine atoms on semiconductor nanosheets [588]. Hydrogenated nanosheets of SiC, GeC, SnC, AlN, BN
and GaN, and fluorinated GaN showed ferromagnetic behavior while fluorinated nanosheets exhibited
antiferromagnetic behavior. Antiferromagnetic and magnetic behavior of nanosheets is credited to the
bond spin polarization and p–p interaction [588,589]. Fig. 35 represents the density of state of hydro-
genated nanosheets in ferromagnetic spin state. SiC 2D monolayer is a wide band semiconductor and
non-magnetic in nature (ionic compound), armchair nanoribbons also shows the ionic character [590].
Charge is transferred from Si atoms to the carbon atoms in SiC. It is interesting to mention that Si
vacancy in the planer honeycomb structure or substitution of Si or C atoms by As, P, B or N induce
the magnetic moment in SiC 2D nanosheet [590]. On the other hand, C, Si + C vacancy or creation of
Si–C antisite unable to develop any magnetic movement. It can be concluded from these studies that
Fig. 34. Summary of possible binary compounds of group III–V, II–VI and IIB–VI 2D layered materials exhibiting the structural
stability, band gap and energy of compound formation. H stands for common hexagonal structure, T stands for tetragonal
structure and V stands for buckled inequilateral hexagonal structure with space group PMN21. Stable H, T and V structures have
been color coded with orange, blue and green color while unstable structures with gray color. The energy of formation of
structure increased from top to bottom, therefore, the lower-lying structure in each color coded box is the most stable phase
and the upper-lying structure is the less stable phase. ‘‘+’’ means half-metal and ‘‘⁄’’ means semiconductor. Straight arrow ‘‘"’’
means and slant arrow ‘‘%’’ means indirect band gap [578]. Reprinted by permission of Royal Society of Chemistry publications.
defect type and atom, adatom and its concentration and critical parameters to tune the electronic
structure and magnetic properties of SiC monolayers.
First-principle calculation also predicts the optical properties of SiC monolayer which is
largely affected by the electron–hole orbital interaction due to reduced dimensionality in one plane
[591]. An excitation peak corresponds to 1.17 eV was observed in the optical spectrum. This has
also been proved experimentally from liquid exfoliated SiC nanoflakes which emits light and showed
peat at 373 nm in photoluminescence (PL) spectra due to quantum confinement induced emission
[138].
8.6. Kaolinite (aluminosilicate, Al2Si2O5(OH)4)
Clays are abundantly found in nature as deposits. Among many forms of clays, Kaolinite is the most
abundant clay mineral in nature. Classical kaolinite is mined as thick plates in books composed of 20–
60 nm thick pseudo-hexagonal, plate shaped crystals [592]. A single crystal layer of kaolinite is com-
posed of one layer of silica tetrahedral with four apical oxygen and another layer of alumina octahe-
dral. Two apical oxygen of alumina octahedral is shared with silica and four apical hydroxyl groups
(OH) (Fig. 36a). Hence, the stoichiometric ratio of silica and alumina layers is always remains 1:1
[593,594]. Kaolinite has a unit cell of 5.14 Å 8.83 Å 7.37 Å expends in xy plane, whereas these
Fig. 35. Density of state of hydrogenated nanosheets in ferromagnetic spin state from first principle calculation. Reprinted from
Ref. [588] with permission of Elsevier Publishers.
sheets stack in z direction by weak hydrogen bonding between OH of alumina of one sheet and oxygen
of the silica to the next [595].
8.6.1. Physicochemical properties of Kaolinite

The most interesting feature of nanokaolinite sheet is its electrokinetic behavior due to the surface
charge on edge surfaces and in basal plane surfaces (assumed 001 and 001 for silica tetrahedral and
alumina octahedral layers, respectively). The electrokinetic behavior of kaolinite suspension changes
with the pH, it is assumed that basal planes have a negative charge, whereas edges have a positive and
negative charge with varying pH, thus eliminating the possibility of surface charge dependency on
suspension pH for basal planes. In order to resolve this discrepancy, several attempts have been car-
ried out to understand the surface chemistry of kaolinite nanoparticles. Chassange et al. [596] used
electrophoresis and complex conductivity measurement together to analyze the zeta potential and
stern layer conductance on kaolinite. This study showed the dependence of electrophoretic mobility
with varying pH and ionic strength, but failed to correlate stern layer conductance with ion mobility
and chemical reactions. Another study took the account of the strain in planer silicate layer due to the
lattice mismatch in the silica tetrahedral and alumina octahedral, thus affect the electro kinetic behav-
ior [597]. The point of zero charge (PZC) for kaolinite was determined at pH 3.5. This study also
stressed on the further investigation on the wetting of silica tetrahedral face of kaolinite despite the
absence of reversed polarity, whereas evidence showed the hydrophobic nature of silica tetrahedral
face for pyrophillite. Recently it has been measured that the surface charge of alumina octahedral
and silica tetrahedral faces of kaolinite from AFM [592]. Kaolinite particles were placed on positively
Fig. 36. (a) Atomic model representation of crystal structure of kaolinite [607]. (b) Surface potential of alumina octahedral and
silica tetrahedral faces of kaolinite as a function of pH [592]. (c) Tofel curve and (d) impedance curve of P(2,3-DMA)-kaolinite
composite coating processed by in-situ polymerization and conventional mixing [594]. (e) Current intensity variation with
different size of anions [608]. (f) UV–Vis spectra of PVC–kaolinite composite at different loading of PVC showing absorbance
peak at 265 nm [600]. Reprinted by permission of American Chemical Society, Elsevier, and Royal Society of Chemistry
Publishers.
and negatively charged surfaces and surface forces were measured between the silicon nitride tip and
faces at different solution pH ranging from 4 to 10 in 1 mM KCl as background electrolyte. Results
exhibit the ambipolar nature of kaolinite particles as a strong function of pH (Fig. 36b). Alumina sur-
face shows positive charge at pH < 6, whereas the silica surface of kaolinite remains negative at pH > 4.
It can be interpreted from these findings that PZC for alumina and silica faces of kaolinite is at pH 6–8
and pH < 4, respectively. Alternative alumina octahedral-silica tetrahedral layered structure,
hexagonal plate like morphology and surface chemistry to make it suitable for numerous applications
which are discussed in the next section.
8.6.2. Applications
Pristine properties of graphene and other 2D layered material such as MoS2, WS2 have shown
potential for 2D materials in electronic and optoelectronic applications. In contrast to that kaolinite
has found widespread application in polymer based composites for enhanced mechanical performance
[598], tribological behavior [599], corrosion resistance [594], thermal and optical properties [600]
attributed to its high crystallinity and distinctive structure. Kaolinite has been used both as reinforce-
ment and matrix phase with polymers such as poly(2,3-dimethylaniline) [594,601], epoxy [602],
polypropylene and polystyrene [603], polyaniline [604] etc. This long list of polymers ranging from
thermosetting to thermoplastic, conducting to insulating suggest the compatibility of kaolinite with
almost all classes of polymer. The intercalation of monomer into kaolinite and their in-situ polymer-
ization method is a promising technique to synthesize nanocomposites [605]. Recently, researchers
[594] used DMSO and methanol to intercalate kaolinite followed by replacement of methanol by
2,3-DMA monomer. After intercalation of kaolinite from 2,3-DMA monomer, ammonium persulfate
(APS) was used as oxidant. This nanocomposite coating has shown enhanced corrosion resistance
and thermal stability in 3.5% NaCl solution (Fig. 36c and d). Changing the polymer to polyaniline
and potassium dichromate as oxidant, kaolinite/polyaniline nanocomposite have been developed by
in-situ intercalation–polymerization which has a temperature sensing properties in 5–120 °C tem-
perature range [604]. The resistivity of the composite is a function of temperature and increase with
increasing temperature. This study also demonstrates that the amount of polyaniline does not depend
on the size of kaolinite particle size whereas conductivity does. This in-situ intercalation-grafting
method also has been utilized to mimic the microstructure of Nacre (sea shell) which composed of
98% calcium carbonate and 2% binder displays excellent toughness due to its interlocked layered
structure [598].
Selection of the suitable intercalating agent also turns kaolinite nanosheets into nanoscrolls.
Intercalation of nanosheets using alkyltrimethylammonium salts and 1-hexadecyl-3-methylim-
idazolium chloride result of the fading interaction between guest species and interlayer surface of
methoxy-modified kaolinite followed by swelling [606]. However, pretreatment of kaolinite is
required for the transformation. This transformation not only changes the morphology of kaolinite,
but also open new avenue for kaolinite as a template for the preparation of 1D arrays and mesoporous
materials. Kaolinite nanosheets can also be used as support for sensors for magnetic field detection
and super capacitor. Distribution of super-paramagnetic iron oxide nanoparticles over nanosheets fol-
lowed by alignment of kaolinite-iron oxide system in the magnetic field. Strength of magnetic field can
be measured by the change in the orientation of naosheets.
Kaolinite has also been utilized to detect the anions of different sizes by screening the anions to
pass through the basal plane spacing via an anion exchange process [608]. To synthesize the electro-
chemical sensor, kaolinite is modified by grafting ionic liquids of different size, which increases the
spacing between the basal planes in kaolinite. Thin film of modified kaolinite is deposited on carbon,
which acted as working electrode in cyclic voltammetry. When varying size of anions passes through
the anionic exchange process in the basal plant, changes in the intensities are recorded (Fig. 36e). This
ionic size based sensor could be implicated for the detection of virus and bacteria for water resource
health monitoring. UV transmission has also been observed in the DMSO modified kaolinite–PVC com-
posite at 265 nm (Fig. 36f) [600].
Due to its distinctive silica tetrahedral and alumina octahedral layers, kaolinite nanosheets also
behave as Janus like particles. Therefore, different type of reactions can occur in basal planes because
of different interfacial activity. Recently, researchers [609] prepared PS–Kaolinite–PMMA blend via
modification of octahedral (hydrophilic side) and tetrahedral (hydrophobic side) basal plane using
PCM copolymer having catechol group and PDPS copolymer, respectively. In the next step, PMMA
was covalently anchored with the catechol group on octahedral side and tetrahedral side was modi-
fied by cation exchange with PS. These particles have application in stabilizers in emulsion, reversibil-
ity of cluster formation, size control, self-assembly of nanoparticles, water repellent fibers etc.
9. Future prospects and concluding remarks
The inventions of the current century are known to be nanotechnology, information technology and
biotechnology. Nanotechnology covers several branches in which two dimensional nanostructured
materials (2D NSMs) have covered numerous developments in both fundamental and applied sciences.
Nanoplates, nanosheets, nanowalls, nanodisks etc, are considered in the category of 2D NSMs. More or
less all types of materials have been used to develop 2D NSMs, such as organics, ceramics, metals, and
semiconductors. However, layered materials and nanosheets are the most extensively studied 2D NSMs
because of their unique physicochemical properties. This review article explains the current advance-
ment in the production and fabrication of 2D NSMs beyond graphene. In principle, graphene could be
an ideal structure used to study the essential physicochemical properties of various 2D NSMs and their
applications. Currently, the topic of 2D materials beyond graphene is one of the greatest dynamic
research fields in nanoscience moving at a rapid pace. The finding of 2D NSMs indicates that these
materials exhibit either similar physical properties or strikingly different electronic properties to gra-
phene. Knowing that 2D materials have unique physical and chemical properties that are more signifi-
cantly separated from their bulk counterpart and can be modified by strain energy, chemical doping,
and electric field to improve the original properties of 2D materials for many technological applica-
tions. These 2D layered structure materials with high surface area, versatile, excellent optical and elec-
tronic properties will be potentially very useful for application in MEMS and NEMS electronic devices,
biosensors, lithium ion batteries, super capacitors, solar cells, and catalysts.
Even though the theoretical studies explains the electronic properties of TMD layers, BN
nanosheets, germanene and silicene, the other physical properties such as mechanical, optical, chemi-
cal and thermal properties of these 2D materials remain undiscovered. At this time of the review, there
are only few theoretical investigations on TMDs and metal chalcogenides. Hopefully, the unique prop-
erties of these metal chalcogenides and TMDs explained by theoretical studies will accelerate further
experimental investigation. Experimental technique for large-scale production of mono-layer and
multi-layer samples of these 2D NSMs does not exist at the present point in time other than BN
nanosheets and graphene. Hence, it is important to prepare 2D materials beyond graphene with fixed
number of layers with large areas. There are many methods to prepare these 2D NSM materials apart
from exfoliation techniques, such as chemical vapor deposition (CVD), van der Waals epitaxial growth
on substrate, and hydrothermal synthesis. These experimental techniques are feasible because of their
possible evidence presented herein. For instance, CVD growth of mono- and multi-layer BN
nanosheets and multi-layer MoS2, van der Waals growth of h-BN, hexagonal Si, and MoS2 layers on
substrate, hydrothermal synthesis of h-BN, MoS2, and MoSe2.
The direct band gap is one of the interesting properties of single layer MoS2 and WS2 materials. This
TMD’s direct band gap is different from graphene and also from their two layers, multilayer, and bulk
phases. Within the band gap, single layer MX2 transistor performance is much better than the avail-
able silicon transistor, when a thin dielectric film is used. The PL emission of mechanically exfoliated
single layer MoS2 nanosheets was very strong compare to multilayer MoS2 sheets. The direct band gap
is the main reason for strong PL emission in single layer MoS2 nanosheets, which is not present in the
crystalline silicon material. This extraordinary result combined with spin–orbit coupling, contributes
to valley and coupled spin physics in single layers of TMDs. These results designates that TMD semi-
conducting single layer nanosheets offers innovative and stimulating opportunities for electronic
industries. Even though there are many experimental studies available on 2D MoS2 nanosheets, but
a very limited number of studies discussed about metal chalcogenides nanosheets on their optical
and electronic properties.
According to theoretical evaluation, germanene and silicene are more active materials and express
similar electronic properties to graphene. Although there are many theoretical studies explains the
structural and electronic properties of germanene and silicene, but experimental studies on those
two materials are limited. At present, most of the germanene and silicene 2D layer materials are estab-
lished on metallic substrates. However, these metallic substrates are not appropriate for electronic
device fabrication. Therefore at present, bigger endeavors are taken to establish germanene and sil-
icene on non-metallic or on insulating substrates at large scale.
Unlike silicene and germanene, oxide and hydroxide nanosheets have been studied experimentally
and are rich in electronic, magnetic and catalytic properties. These nanosheets have been successfully
exfoliated and assembled into nano-architectured films on variety of substrates credited to their
charged nature. Due to their superior leakage current characteristic and insulating behavior, these
nanosheets have found berth in the future electronic devices as it could be possible to bring down
the technology nodes in the semiconductor industry by employing these nanosheets. Moreover, oxide
and hydroxide nanosheets have also found opportunities in magneto-optical and spintronic devices as
ferromagnetic behavior have been demonstrated. Unique structure of kaolinite, alumina octahedra on
one side and silica tetrahedra on the other side of basal plane, have resulted in distinct electrokinetic
behavior at different pHs which make it possible to intercalate several different type of polymer and
foreign species into the interlayer galleries. Therefore, in-situ intercalated polymer-kaolinite
nanocomposites have found a wide variety of application in sensors, optical, thermal stability, and cor-
rosion protection.
Although, the investigation of 2D materials beyond graphene is still in its early phase, however, the
extraordinary properties of these 2D materials can afford fascinating new opportunities for scientists
and engineers to increase the research activities in this rapidly developing field. The potential areas
towards fundamental investigation are numerous including the improvement and development of
new efficient techniques to produce 2D nanosheets with specific number of layers and enhancing
the structural excellence of the developed layers. The investigation of the essential physicochemical
properties of single- and multi-layer nanosheets, the production of interfacial properties among the
heterojunctions; and enhancement of fundamental physicochemical properties by doping, strain
effect, electric field, and functionalization are all open for future research. Moreover, the various
opportunities for producing new 2D nanostructured materials with interesting properties will make
them a viable material for future research that will benefit the industries and ultimately our society.
Acknowledgements
Prof. Seal acknowledge the financial support from National Science Foundation (NSF), National
Institute of Health (NIH), various Industries and Florida high tech corridor funding nanotechnology
and materials research. Authors convey their sincere thanks to the anonymous reviewer for their con-
structive comments.
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Recent Development in 2D Materials Beyond Graphene

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Progress in Materials Science 73 (2015) 44–126

Contents lists available at ScienceDirect

Progress in Materials Science

Recent development in 2D materials beyond

2.1. Zero dimensional (0D) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

9. Future prospects and concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

NFC nanoﬁbrillated cellulose

2. Classiﬁcation of materials based on dimension

2.1. Zero dimensional (0D)

2.2. One dimensional (1D)

2.3. Two dimensional (2D)

2.4. Three dimensional (3D)

4.1. Layered van der Waals solids

4.2. Layered ionic solids

4.3. Surface assisted nonlayered solids

5. Synthesis methods for 2D materials

5.1. Micromechanical exfoliation using scotch tape

5.2. Liquid exfoliation

As discussed in the previous section, mechanical exfoliation of 2D layered materials is a semi-

5.3. Chemical vapor deposition (CVD)

5.4. Van der Waal epitaxial growth on substrate

5.5. Hydrothermal synthesis

Examining the vibrational and molecular structure of 2D nanostructured materials is integrally

6.1. Microscopy techniques for 2D materials

6.1.1. Atomic force microscopy

6.1.2. Ultrasonic force microscopy

6.1.3. Electron microscopy techniques

6.2. Raman spectroscopy

6.3. Photoluminescence (PL) spectroscopy

6.4. X-ray diffraction

X-ray diffraction (XRD) is a non-destructive analytical characterization method to determine the

6.5. Characterization possibilities

7.1. Mechanical properties of 2D materials

7.2. Bulge test

Dp:pR2 ¼ r 2pRt ð4Þ

where W is the length along the short end of the rectangle.

7.4. Contact adhesion

Contact adhesion is an essential mechanical property of 2D materials and an interesting area of

7.5. Blister test

7.6. Van der Waals force

8. 2D materials, their properties, and application

8.1. TMD layers

S (eV) Se (eV) Te (eV)

8.1.1. Synthesis of TMD layers (MoS2 and WS2)

8.1.2. Physical properties of MoS2 and WS2

8.1.3. Functionalization of TMDs

8.1.4. Applications of MoS2 and WS2

8.2. Hexagonal Boron Nitride (h-BN)

8.2.2. Physical properties of BNNS

8.2.3. Wide band gap modiﬁcation

8.2.4. Thermal conductivity of BNNS

8.2.5. Mechanical property of BNNS

8.2.6. Functionalization of BNNS

8.2.7. Application of h-BN

8.3. Silicene and germanene

8.3.1. Structural and electronic properties of silicene and germanene

8.3.2. Functionalized silicene and germanene

2D nanosheet Method Eg (eV) Type of Magnetic Ref.

8.4. 2D layered oxide and hydroxide

8.4.2. Assembly of 2D nanosheets