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Transition metal

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(a) Structure of a hexagonal TMD monolayer. M

atoms are in black and X atoms are in yellow. (b) A
hexagonal TMD monolayer seen from above.
Transition metal dichalcogenide (TMD)
monolayers are atomically thin
semiconductors of the type MX2, with M
a transition metal atom (Mo, W, etc.) and
X a chalcogen atom (S, Se, or Te). One
layer of M atoms is sandwiched between
two layers of X atoms. They are part of
the large and new family of the so-called
2D materials, name used to emphasize
their extraordinary thinness. For example
a MoS2 monolayer is only 6.5 Å thick.
The key feature of these materials is the
interaction of large atoms in the 2D
structure as compared with first-row
transition metal dichalcogenides, e.g.,
WTe2 exhibits anomalous giant
magnetoresistance and

The discovery of graphene shows how

new physical properties emerge when a
bulk crystal of macroscopic dimensions
is thinned down to one atomic layer. Like
graphite, TMD bulk crystals are formed of
monolayers bound to each other by Van-
der-Waals attraction. TMD monolayers
have properties that are distinctly
different from those of the semimetal

TMD monolayers MoS2, WS2, MoSe2,

WSe2, MoTe2 have a direct band gap,
and can be used in electronics as
transistors and in optics as emitters
and detectors.[2][3][4][5][6]
The TMD monolayer crystal structure
has no inversion center, which allows
to access a new degree of freedom of
charge carriers, namely the k-valley
index, and to open up a new field of
physics: valleytronics[7][8][9][10]
The strong spin-orbit coupling in TMD
monolayers leads to a spin-orbit
splitting [11] of hundreds meV in the
valence band and a few meV in the
conduction band, which allows control
of the electron spin by tuning the
excitation laser photon energy and
The work on TMD monolayers is an
emerging research and development field
since the discovery of the direct
bandgap[2][3] and the potential
applications in electronics[4] and valley
physics.[8][9][10] TMDs are often combined
with other 2D materials like graphene
and hexagonal boron nitride to make van
der Waals heterostructure. These
heterostructures need to be optimized to
be possibly used as building blocks for
many different devices such as
transistors, solar cells, LEDs,
photodetectors, fuel cells, photocatalytic
and sensing devices. Some of these
devices are already used in everyday life
and can become smaller, cheaper and
more efficient by using TMD
monolayers.[13][14] Others are still being
developed and promise to have a huge
impact on our technology.

Crystal structure

Primitive cell of WSe2

In the macroscopic bulk crystal, or more

precisely, for an even number of
monolayers, the crystal structure has an
inversion center. In the case of a
monolayer (or any odd number of layers),
the crystal has no inversion center. Two
important consequences of that are:

nonlinear optical phenomena, such as

second-harmonic generation. When
the crystal is excited by a laser, the
output frequency can be
an electronic band structure with direct
energy gaps, where both conduction
and valence band edges are located at
the non-equivalent K points (K+ and K-)
of the 2D hexagonal Brillouin zone. The
interband transitions in the vicinity of
the K+ (or K-) point are coupled to right
(or left) circular photon polarization
states. These so-called valley
dependent optical selection rules arise
from inversion symmetry breaking.
This provides a convenient method to
address specific valley states (K+ or
K-) by circularly polarized (right or left)
optical excitation.[10] In combination
with strong spin-splitting, the spin and
valley degree of freedom are coupled,
enabling stable valley

These properties indicate that TMD

monolayers represent a promising
platform to explore spin and valley
physics with the corresponding possible
Transport properties

Representative scheme of the section of a field

effect transistor based on a monolayer of MoS2[4]

At submicron scales, 3D materials no

longer have the same behavior as their
2D form, which can be an advantage. For
example, graphene has a very high carrier
mobility, and accompanying lower losses
through the Joule effect. But graphene
has zero bandgap, which results in a
disqualifyingly low on/off ratio in
transistor applications. TMD monolayers
might be an alternative: they are
structurally stable, display a band gap
and show electron mobilities comparable
to those of silicon, so they can be used to
fabricate transistors.

In 2004, the first field-effect transistor

(FET) made of bulk WSe2 was reported. It
showed a mobility below 500 cm2 V−1 s−1
for p-type conductivity at room
temperature, about half that of a silicon
FET but a low on/off current ratio
because the device was realised on the
surface of a bulk crystal. FETs made of
monolayer MoS2 showed an excellent
on/off ratio exceeding 108.[4]

High carrier mobility, high on/off ratio

and small thickness (one monolayer) of
TMD devices are potentially interesting
for such applications.

Optical properties
Theoretical transition energy[22]
A (eV) A (nm) B (eV) B (nm)

MoS2 1.78 695 1.96 632

MoSe2 1.50 825 1.75 708


WS2 1.84 673 2.28 544

WSe2 1.52 815 2.00 619

A semiconductor can absorb photons

with energy larger than or equal to its
bandgap. This means that light with a
shorter wavelength is absorbed.
Semiconductors are typically efficient
emitters if the minimum of the
conduction band energy is at the same
position in k-space as the maximum of
the valence band, i.e., the band gap is
direct. The band gap of bulk TMD
material down to a thickness of two
monolayers is still indirect, so the
emission efficiency is lower compared to
monolayered materials. The emission
efficiency is about 104 greater for TMD
monolayer than for bulk material.[5] The
band gaps of TMD monolayers are in the
visible range (between 400 nm and
700 nm). The direct emission shows two
transitions called A and B, separated by
the spin-orbit coupling energy. The
lowest energy and therefore most
important in intensity is the A
emission.[2][23] Owing to their direct band
gap, TMD monolayers are promising
materials for optoelectronics

Representative scheme of the section of an

ultrasensitive Photodetector based on a monolayer
of MoS2[6]
Atomic layers of MoS2 have been used
as a phototransistor and ultrasensitive
detectors. Phototransistors are
important devices: the first with a MoS2
monolayer active region shows a
photoresponsivity of 7.5 mA W−1 which is
similar to graphene devices that reach
6.1 mA W−1. Multilayer MoS2 show
higher photoresponsivities, about 100
mA W−1, which is similar to silicon
devices. Making a gold contact at the far
edges of a monolayer allows an
ultrasensitive detector to be fabricated.[6]
Such a detector has a photoresponsivity
reaching 880 A W−1, 106 greater than the
first graphene photodetectors. This high
degree of electrostatic control is due to
the thin active region of the monolayer.
Its simplicity and the fact that it has only
one semiconductor region, whereas the
current generation of photodetectors is
typically a p-n junction, makes possible
industrial applications such as high-
sensitivity and flexible photodetectors.
The only limitation for currently available
devices is the slow photoresponse

Mechanical properties

A monolayer of MoS2 can be strained at

least up to 10%,[24] comparable to
graphene. Under the application of strain,
a decrease in the direct and indirect band
gap is measured that is approximately
linear with strain.[25] Importantly, the
indirect bandgap decreases faster with
applied strain to the monolayer than the
direct bandgap, resulting in a crossover
from direct to indirect band gap at a
strain level of around 1%.[26] As a result,
the emission efficiency of monolayers is
expected to decrease for highly strained
samples.[27] This property allows
mechanical tuning of the electronic
structure and also the possibility of
fabrication of flexible electronics i.e. on
flexible substrates.

Fabrication of TMD

Exfoliation is a top down approach. In the

bulk form, TMDs are crystals made of
layers, which are coupled by Van-der-
Waals forces. These interactions are
weaker than the chemical bonds
between the Mo and S in MoS2, for
example. So TMD monolayers can be
produced by micromechanical cleavage,
just as graphene.

The crystal of TMD is rubbed against the

surface of another material (any solid
surface). In practice, adhesive tape is
placed on the TMD bulk material and
subsequently removed. The adhesive
tape, with tiny TMD flakes coming off the
bulk material, is brought down onto a
substrate. On removing the adhesive
tape from the substrate, TMD monolayer
and multilayer flakes are deposited. This
technique produces small samples of
monolayer material, typically about 5–10
micrometers in diameter.[28]

Large quantities of exfoliated material

can also be produced using liquid-phase
exfoliation by blending TMD materials
with solvents and polymers.[29]

Chemical vapor deposition

Chemical vapor deposition is a bottom-

up approach. For example, the synthesis
of MoS2 is made using: SiO2 as a
substrate, MoO3 and S powders used as
reactants. The reactants are delivered on
the substrate and the whole is heated to
650 Celsius degrees in the presence of
N2. The size of the sample is larger than
obtained with the exfolation

Molecular beam epitaxy

Molecular beam epitaxy (MBE) is an

established technique for growing
semiconductor devices with atomic
monolayer thickness control. As a
promising demonstration, high-quality
monolayer MoSe2 samples have been
grown on graphene by MBE.[31]

Electronic band structure

Band gap

In the bulk form, TMD have an indirect

gap in the center of the Brillouin zone,
whereas in monolayer form the gap
becomes direct and is located in the K

Spin-orbit coupling
Theorical energy of the spin-orbit coupling[32][33]
Valence band Conduction band

splitting (eV) splitting (eV)

MoS2 0.148 0.003

WS2 0.430 0.026

MoSe2 0.184 0.007

WSe2 0.466 0.038

MoTe2 0.219 0.034

For TMDs, the atoms are heavy and the

outer layers electronic states are from d-
orbitals that have a strong spin-orbit
coupling. This spin orbit coupling
removes the spins degeneracy in both
the conduction and valence band i.e.
introduces a strong energy splitting
between spin up and down states. In the
case of MoS2, the spin splitting in
conduction band is in the meV range, it is
expected to be more pronounced in other
material like WS2.[34][35][36] The spin orbit
splitting in the valence band is several
hundred meV.

Spin-valley coupling and the

electron valley degree of

Spin splittings and optical selection rules[33]

Photoluminescence (PL) of a MoS2 monolayer at 4 K
excited by a σ+ polarized laser. The monolayer
absorbs the incident light and re-emits it at lower
energy. The energy of the peak center correspond to
the optical gap.

By controlling the charge or spin degree

of freedom of carriers, as proposed by
spintronics, novel devices have already
been made. If there are different
conduction/valence band extrema in the
electronic band structure in k-space, the
carrier can be confined in one of these
valleys. This degree of freedom opens up
a new field of physics: the controlling of
carriers k-valley index, also called

For TMD monolayers crystals, the parity

symmetry is broken, there is no more
inversion center. K valleys of different
directions in the 2D hexagonal Brillouin
zone are no longer equivalent. So there
are two kinds of K valley called K+ and K-.
Also there is a strong energy degeneracy
of different spin states in valence band.
The transformation of one valley to
another is described by the time reversal
operator. Moreover, crystal symmetry
leads to valley dependent optical
selection rules: a right circular polarized
photon (σ+) initializes a carrier in the K+
valley and a left circular polarized photon
(σ-) initializes a carrier in the K- valley.[8]
Thanks to these two properties (spin-
valley coupling and optical selection
rules), a laser of specific polarization and
energy allows to initialize the electron
valley states (K+ or K-) and spin states
(up or down).[1]

Emission and absorption of

light: excitons

A single layer of TMD can absorb up to

20% of incident light,[6] which is
unprecedented for such a thin material.
When a photon of suitable energy is
absorbed by a TMD monolayer, an
electron is created in the conduction
band; the electron now missing in the
valence band is assimilated by a
positively charged quasi-particle called a
hole. The negatively charged electron
and the positively charged hole are
attracted via the Coulomb interaction,
forming a bound state called an exciton
which can be thought as an hydrogen
atom (with some difference). This
Bosonic-like quasi-particle is very well
known and studiend in traditional
semiconductors, such as GaAs and ZnO
but in TMD it provides exciting new
opportunities for applications and for
studying fundamental physics. Indeed,
the reduced dielectric screening and the
quantum size effect present in these
ultrathin materials make the binding
energy of excitons much stronger than
those in traditional semiconductors.
Binding energies of several hundreds of
meV are observed for all the four
principal members of the TMD

E l l di f it if it
Energy level diagram of an exciton as if it were an
hydrogen atom.[40]

As mentioned before, we can think about

an exciton as if it were a hydrogen atom,
with an electron bound to a hole. The
main difference is that this system is not
stable and tends to relax to the vacuum
state, which is here represented by an
electron in the valence band. The energy
difference between the exciton 'ground
state' (n=1) and the 'vacuum state' is
called optical gap and is the energy of
the photon emitted when an exciton
recombines. This is the energy of the
photons emitted by TMD monolayers and
observed as huge emission peaks in
photoluminescence (PL) experiments,
such as the one labelled X0 in the figure.
In this picture the binding energy EB is
defined as the difference between the
free particle band gap and the optical
band gap and represent, as usual, the
energy needed to take the hole and the
electron apart. The existence of this
energy difference is called band gap
renormalization. The analogy with
hydrogen atom doesn't stop here as
excitonic excited states were observed at
higher energies and with different

Because of the spin-orbit splitting of the

valence band two different series of
excitons exist in TMD, called A- and B-
excitons. In the A series the hole is
located in the upper branch of the
Valence band while for the B-exciton the
hole is in the lower branch. As a
consequence the optical gap for B-
exciton is larger and the corresponding
peak is found at higher energy in PL and
reflectivity measurements.

Another peak usually appears in the PL

spectra of TMD monolayers, which is
associated to different quasi-particles
called trions.[41][42] These are excitons
bound to another free carrier which can
be either an electron or a hole. As a
consequence a trion is a negative or
positively charged complex. The
presence of a strong trion peak in a PL
spectrum, eventually stronger than the
peak associated with exciton
recombination, is a signature of a doped
monolayer. It is believed now that this
doping is extrinsic, which means that it
arises from charged trap states present
in the substrate (generally SiO2).
Positioning a TMD monolayer between
two flakes of hBN removes this extrinsic
doping and greatly increase the optical
quality of the sample.[40][43]

At higher excitation powers

biexcitons[44][45] have also been observed
in monolayer TMDs. These complexes
are formed by two bound excitons.
Theory predicts that even larger charge-
carrier complexes, such as charged
biexcitons (quintons) and ion-bound
biexcitons, are stable and should be
visible in the PL spectra.[46]

Graphene-MoS2 enhanced SPR biosensor.[47]

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