crystals

Review
Synthesis Methods of Two-Dimensional MoS2:
A Brief Review
Jie Sun 1,2, *, Xuejian Li 1 , Weiling Guo 1 , Miao Zhao 3 , Xing Fan 1 , Yibo Dong 1 , Chen Xu 1 ,
Jun Deng 1 and Yifeng Fu 4, *
1 Key Laboratory of Optoelectronics Technology, College of Microelectronics, Beijing University of Technology,
Beijing 100124, China; [email protected] (X.L.); [email protected] (W.G);
[email protected] (X.F.); [email protected] (Y.D.); [email protected] (C.X.);
[email protected] (J.D.)
2 Quantum Device Physics Laboratory, Department of Microtechnology and Nanoscience,
Chalmers University of Technology, Göteborg 41296, Sweden
3 High-Frequency High-Voltage Device and Integrated Circuits Center, Institute of Microelectronics,
Chinese Academy of Sciences, Beijing 10029, China; [email protected]
4 Electronics Material and Systems Laboratory, Department of Microtechnology and Nanoscience,
Chalmers University of Technology, Göteborg 41296, Sweden
* Correspondence: [email protected] (J.S.); [email protected] (Y.F.)

Academic Editor: Filippo Giannazzo

Received: 19 May 2017; Accepted: 28 June 2017; Published: 1 July 2017

Abstract: Molybdenum disulfide (MoS2 ) is one of the most important two-dimensional materials after
graphene. Monolayer MoS2 has a direct bandgap (1.9 eV) and is potentially suitable for post-silicon
electronics. Among all atomically thin semiconductors, MoS2 ’s synthesis techniques are more
developed. Here, we review the recent developments in the synthesis of hexagonal MoS2 , where they
are categorized into top-down and bottom-up approaches. Micromechanical exfoliation is convenient
for beginners and basic research. Liquid phase exfoliation and solutions for chemical processes are
cheap and suitable for large-scale production; yielding materials mostly in powders with different
shapes, sizes and layer numbers. MoS2 films on a substrate targeting high-end nanoelectronic
applications can be produced by chemical vapor deposition, compatible with the semiconductor
industry. Usually, metal catalysts are unnecessary. Unlike graphene, the transfer of atomic layers is
omitted. We especially emphasize the recent advances in metalorganic chemical vapor deposition
and atomic layer deposition, where gaseous precursors are used. These processes grow MoS2 with
the smallest building-blocks, naturally promising higher quality and controllability. Most likely, this
will be an important direction in the field. Nevertheless, today none of those methods reproducibly
produces MoS2 with competitive quality. There is a long way to go for MoS2 in real-life electronic
device applications.

Keywords: Molybdenum disulfide; transition metal dichalcogenide; two-dimensional materials;

micromechanical exfoliation; chemical vapor deposition.

1. Introduction
Recently, graphene has received considerable attention in scientific communities. It is recognized
as a new wonder material (e.g., record carrier mobility, thermal conductivity, mechanical strength and
flexibility), and applications in nanocomposites, paints, transparent electrodes, heat spreaders, etc. are
being explored [1]. However, one should not forget that the original motivation for studying graphene
was in its field effect [2], with a hope that it might play a key role in nanoelectronics, rather than
serving as a passive element such as electrodes [3]. Nevertheless, at this stage, due to the difficulties in

Crystals 2017, 7, 198; doi:10.3390/cryst7070198 www.mdpi.com/journal/crystals

Crystals 2017, 7, 198 2 of 11

opening an energy bandgap in graphene, it is not clear whether graphene will become a key material
in electronics at all. Therefore, the search for other two-dimensional (2D) materials (materials with
Crystals 2017, 7, 198 2 of 10
one or few atomic layers) with an inherent energy bandgap that is suitable to make transistors is
essential. Black phosphorus [4], transition metal dichalcogenide (TMD) [5], gallium nitride [6], etc.
bandgap that is suitable to make transistors is essential. Black phosphorus [4], transition metal
are extensively explored. For any type of application, the material production is always the first
dichalcogenide (TMD) [5], gallium nitride [6], etc. are extensively explored. For any type of
experimental step. Among these 2D semiconductors, molybdenum disulfide (MoS ) is relatively more
application, the material production is always the first experimental step. 2Among these 2D
mature in terms of its synthesis technologies. Hence, in this paper, we provide a short literature
semiconductors, molybdenum disulfide (MoS2) is relatively more mature in terms of its synthesis
survey of recent progresses in the synthesis of MoS2 . The paper focuses only on the production
technologies. Hence, in this paper, we provide a short literature survey of recent progresses in the
techniques rather than serving as a complete review on MoS2 -related physics, materials and electronics.
synthesis of MoS2. The paper focuses only on the production techniques rather than serving as a
Also, we put special emphasis on the recent achievements in metalorganic chemical vapor deposition
complete review on MoS2-related physics, materials and electronics. Also, we put special emphasis
(MOCVD) and atomic layer deposition (ALD), where gaseous precursors are used to grow MoS .
on the recent achievements in metalorganic chemical vapor deposition (MOCVD) and atomic layer2
It has a high potential for producing MoS2 with better quality and controllability for nanoelectronic
deposition (ALD), where gaseous precursors are used to grow MoS2. It has a high potential for
device applications.
producing MoS2 with better quality and controllability for nanoelectronic device applications.
2. Synthesis Methods of MoS2
2. Synthesis Methods of MoS2
MoS2 has several polymorphs, where the 2H MoS2 has a layered hexagonal structure with lattice
MoS2 has several polymorphs, where the 2H MoS2 has a layered hexagonal structure with
parameters of a = 0.316 nm and c = 1.229 nm [7], yielding an inter-layer spacing of 0.615 nm [8], as
lattice parameters of a = 0.316 nm and c = 1.229 nm [7], yielding an inter-layer spacing of 0.615 nm [8],
schematically shown in Figure 1. Bulk 2H MoS2 is an indirect bandgap semiconductor (~1.29 eV).
as schematically shown in Figure 1. Bulk 2H MoS2 is an indirect bandgap semiconductor (~1.29 eV).
With decreasing thickness, the bandgap increases. When it comes to monolayer MoS2 , it becomes a
With decreasing thickness, the bandgap increases. When it comes to monolayer MoS2, it becomes a
direct bandgap material, and the energy gap can be as large as ~1.90 eV [9], suitable for fabricating
direct bandgap material, and the energy gap can be as large as ~1.90 eV [9], suitable for fabricating
most electronic devices. The synthesis methods of MoS2 can be divided into top-down and bottom-up
most electronic devices. The synthesis methods of MoS2 can be divided into top-down and
approaches. We hereby describe them in turn.
bottom-up approaches. We hereby describe them in turn.

Figure 1.
Figure Distances between
1. Distances between different
different layers
layers in
in 2H
2H MoS
MoS2..

2.1. Top-down
Top-down Approaches

2.1.1. Micromechanical
2.1.1. Micromechanical Exfoliation
Exfoliation
Similar to
Similar to the
themicromechanical
micromechanicalexfoliation
exfoliationofofgraphene
graphene (a(a vivid
vivid lablab demonstration
demonstration cancan
be be found
found in
in [10]), MoS
[10]), MoS2 flakes
2 flakes can be produced on a substrate using sticky tapes. The starting
can be produced on a substrate using sticky tapes. The starting material is bulk material is bulk
MoS22,, where
MoS where some
some parts
parts are
are peeled
peeled off
off with
with the
the tape
tape and
and pressed
pressed into
into the
the substrate.
substrate. Upon
Upon the
the release
release
of the tape, some parts stay with the substrate rather than the tape due to the
of the tape, some parts stay with the substrate rather than the tape due to the van der Waals forcevan der Waals force
to
to the substrate. Repeating the process may produce flakes of MoS with random
the substrate. Repeating the process may produce flakes of MoS2 2with random shapes, sizes and shapes, sizes and
numbers of
numbers oflayers.
layers.This
Thismethod
method offers 2D2D
offers materials of the
materials of highest quality,
the highest enabling
quality, to study
enabling tothe pristine
study the
properties and ultimate device performances. For example, Kis et al.
pristine properties and ultimate device performances. For example, Kis et al. have used have used micro-exfoliation
to produce MoS2 to
micro-exfoliation monolayers
produce MoS that 2are suitable for
monolayers ultrasensitive
that are suitablephotodetectors
for ultrasensitive[11],photodetectors
analogue [12]
and digital
[11], analoguecircuits [13],digital
[12] and and observation ofand
circuits [13], interesting physics
observation such as mobility
of interesting physicsengineering and a
such as mobility
engineering and a metal–insulator transition [14]. However, it was found that the van der Waals
adhesion of many TMDs to SiO2, a typical substrate, is much weaker than that of graphene.
Therefore, the produced flakes are very small (typically <10 µ m) in their lateral size [15]. These
results notwithstanding, large area MoS2 flakes can be exfoliated by slightly modifying the
technique. Magda et al. obtained mono MoS2 layers with lateral size of several hundreds of microns
Crystals 2017, 7, 198 3 of 11

metal–insulator transition [14]. However, it was found that the van der Waals adhesion of many TMDs
to SiO2 , a typical substrate, is much weaker than that of graphene. Therefore, the produced flakes are
very small (typically <10 µm) in their lateral size [15]. These results notwithstanding, large area MoS2
flakes can be exfoliated by slightly modifying the technique. Magda et al. obtained mono MoS2 layers
Crystals
with 2017, 7,size
lateral 198 of several hundreds of microns by improving the MoS -substrate adhesion, as shown
3 of 10
2
in Figure 2 [15]. The mechanism is that sulfur atoms can bind more strongly to gold than to SiO2 . The
by improving the MoS2-substrate adhesion, as shown in Figure 2 [15]. The mechanism is that sulfur
drawback is that such as-exfoliated MoS2 flakes have to be transferred to another new substrate, since
atoms can bind more strongly to gold than to SiO2. The drawback is that such as-exfoliated MoS2 flakes
in most applications the material is used on insulating substrates. In addition, like their graphene
have to be transferred to another new substrate, since in most applications the material is used on
counterpart, the tape-assisted micromechanical exfoliation method offers very low yield, and it’s not
insulating substrates. In addition, like their graphene counterpart, the tape-assisted micromechanical
possible to scale up for large volume production, therefore MoS2 synthesized by this method is limited
exfoliation method offers very low yield, and it’s not possible to scale up for large volume production,
to fundamental study at lab scale.
therefore MoS2 synthesized by this method is limited to fundamental study at lab scale.

Figure 2.
2. Large area MoS
Large area MoS2 flakes exfoliated with chemically enhanced adhesion to the substrate [15].
Figure 2 flakes exfoliated with chemically enhanced adhesion to the substrate [15].

2.1.2. Liquid Phase Exfoliation

2.1.2. Liquid Phase Exfoliation
Liquid phase exfoliation also starts from bulk MoS2, producing flakes with random shapes,
Liquid phase exfoliation also starts from bulk MoS2 , producing flakes with random shapes, sizes
sizes and number of layers. The quantities, however, are much larger, and the quality lower.
and number of layers. The quantities, however, are much larger, and the quality lower. Roughly,
Roughly, there are 2 routes to exfoliate MoS2 in solution. The first is exfoliation by mechanical means
there are 2 routes to exfoliate MoS2 in solution. The first is exfoliation by mechanical means such as
such as sonication, shearing, stirring, grinding and bubbling [16–21]. The essence is purely physical,
sonication, shearing, stirring, grinding and bubbling [16–21]. The essence is purely physical, although
although some chemistry may still be involved [22–24]. For example, surfactants such as sodium
some chemistry may still be involved [22–24]. For example, surfactants such as sodium deoxycholate
deoxycholate (SDC) bile salt [22] and chitosan [23] may be added to the solution to prevent the
(SDC) bile salt [22] and chitosan [23] may be added to the solution to prevent the exfoliated flakes
exfoliated flakes from recombination. Electrolysis is employed to generate bubbles in some cases
from recombination. Electrolysis is employed to generate bubbles in some cases [24]. It is known
[24]. It is known that fine bubbles can squeeze into material interfaces and exfoliate them [25]. The
that fine bubbles can squeeze into material interfaces and exfoliate them [25]. The yield of this
yield of this method is dramatically improved from tape-assisted exfoliation, but the efficiency is still
method is dramatically improved from tape-assisted exfoliation, but the efficiency is still low for
low for industrial applications. Therefore, a second route by atomic intercalation via solution
industrial applications. Therefore, a second route by atomic intercalation via solution chemistry [26] or
chemistry [26] or electrochemistry [27] has been proposed. Lithium is typically used to intercalate
electrochemistry [27] has been proposed. Lithium is typically used to intercalate between the MoS2
between the MoS2 layers and enlarge the interlayer spacing, easing the following exfoliation by
layers and enlarge the interlayer spacing, easing the following exfoliation by mechanical treatment
mechanical treatment (e.g., sonication). Fan et al. developed a process to exfoliate MoS2 nanosheets
(e.g., sonication). Fan et al. developed a process to exfoliate MoS2 nanosheets very efficiently using
very efficiently using sonication assisted Li intercalation. They found that the complete Li
sonication assisted Li intercalation. They found that the complete Li intercalation with butylithium can
intercalation with butylithium can be effected within 1.5 hours [28]. An example of the MoS2 flakes
be effected within 1.5 hours [28]. An example of the MoS2 flakes synthesized by this method is shown
synthesized by this method is shown in Figure 3. However, this method results in the loss of
in Figure 3. However, this method results in the loss of semiconducting properties due to the structural
semiconducting properties due to the structural changes during Li intercalation. It is reported that
changes during Li intercalation. It is reported that above an annealing temperature of 300 ◦ C, these
above an annealing temperature of 300 °C, these MoS2 flakes can be somewhat recovered [26].
MoS2 flakes can be somewhat recovered [26].
Crystals 2017, 7, 198 4 of 11
Crystals 2017, 7, 198 4 of 10

Figure TEM,SEM
3. TEM,
Figure 3. SEMand
andAFM
AFMimages
imagesofofMoS
MoS 2 flakes
2 flakes
exfoliated
exfoliated byby
Li Li intercalation
intercalation andand sonication
sonication [28].[28].

Liquid phase exfoliation is a simple technology with low cost, producing large quantity 2D
nanosheets with relatively high quality.
quality. Therefore, it is regarded as the most suitable method for the
large-scale
large-scale industrial
industrialproduction
productionofof
one- to few-layer
one- to few-layer2D material flakes
2D material at low
flakes atexpense [29]. It[29].
low expense is worth
It is
noting that liquid
worth noting thatphase
liquidexfoliation can produce
phase exfoliation not onlynot
can produce wetonly
suspensions of flakes or
wet suspensions of dry
flakespowders,
or dry
but macroscopically
powders, continuouscontinuous
but macroscopically thin films thin
as well [30–32].
films as wellOn substrates,
[30–32]. through drop
On substrates, casting
through of
drop
the suspension
casting and drying,
of the suspension MoS
and 2 thin films
drying, MoS2 are
thinprepared
films areby Walia etby
prepared al. Walia
[30–32],et where optical
al. [30–32], and
where
electrical properties can be studied.
optical and electrical properties can be studied.

2.2. Bottom-up Approaches

2.2. Bottom-up Approaches
2.2.1. Physical Vapor Deposition
2.2.1. Physical Vapor Deposition
Although molecular beam epitaxy (MBE) is an advanced technology for growing single crystal
Although molecular beam epitaxy (MBE) is an advanced technology for growing single crystal
semiconductor thin films, its application in producing 2D materials needs further development, and
semiconductor thin films, its application in producing 2D materials needs further development, and
the grain size of the 2D material is not as high as expected [33]. In fact, even ordinary physical vapor
the grain size of the 2D material is not as high as expected [33]. In fact, even ordinary physical vapor
deposition is rare. There is a report on growing MoS2 -Ti composite by vacuum sputtering, using Ti
deposition is rare. There is a report on growing MoS2-Ti composite by vacuum sputtering, using Ti
and MoS2 as the targets [34]. However, the MoS2 is an amorphous structure in this case.
and MoS2 as the targets [34]. However, the MoS2 is an amorphous structure in this case.
2.2.2. Solution Chemical Process
2.2.2. Solution Chemical Process
There are various methods for producing MoS2 by solution chemistry. Hydrothermal
There are various methods for producing MoS2 by solution chemistry. Hydrothermal synthesis [35]
synthesis [35] and solvothermal synthesis [36] typically use molybdate to react with sulfide or just
and solvothermal synthesis [36] typically use molybdate to react with sulfide or just sulfur in a
sulfur in a stainless steel autoclave, where a series of physicochemical reactions take place under
stainless steel autoclave, where a series of physicochemical reactions take place under relatively high
relatively high temperature (e.g., 200 ◦ C) and high pressure for several hours or longer. The resultant
temperature (e.g., 200 °C) and high pressure for several hours or longer. The resultant is MoS2
is MoS2 powders of different shapes. The size of individual particles can be adjusted to some extent.
powders of different shapes. The size of individual particles can be adjusted to some extent. Very
Very frequently, the powders are high-temperature post-annealed, to improve their crystalline quality
frequently, the powders are high-temperature post-annealed, to improve their crystalline quality and
and purity. The only difference between hydrothermal and solvothermal synthesis is that the precursor
purity. The only difference between hydrothermal and solvothermal synthesis is that the precursor
solution in the latter case is usually not aqueous. Other solution chemical processes start at almost
solution in the latter case is usually not aqueous. Other solution chemical processes start at almost room
room temperature and atmospheric pressure, where post-annealing is often used anyway [37–41].
temperature and atmospheric pressure, where post-annealing is often used anyway [37–41]. The
products can be either a powder or thin film, depending on the preparation details. The most
Crystals 2017, 7, 198 5 of 11

The products can be either a powder or thin film, depending on the preparation details. The most
commonly-used
Crystals 2017, 7, precursor
198 is (NH4 )2 MoS4 (ammonium tetrathiomolybdate), or something similar.
5 of 10
◦
(NH4 )2 MoS4 decomposes to form MoO3 at 120–360 C, which can be further converted into MoS2 .
commonly-used precursor is (NH4)2MoS4 (ammonium tetrathiomolybdate), or something similar.
In some cases, electrochemical deposition [42–44] and photo-assisted deposition are used [45]. For
(NH4)2MoS4 decomposes to form MoO3 at 120–360 °C, which can be further converted into MoS2. In
instance,
some Licases,
et al.electrochemical
fabricated MoS 2 nanowires
deposition and
[42–44] andnanoribbons using
photo-assisted MoOxare
deposition as used
the precursor
[45]. For [43].
The MoO ◦
x precursor
instance, is then exposed
Li et al. fabricated to H2 S and
MoS2 nanowires at high temperature
nanoribbons (500–800
using MoO x as the C) to synthesize
precursor [43]. The MoS2 .
Depending
MoOx on the temperature
precursor for processing,
is then exposed to H2S atboth
high2H and 3R phase
temperature of MoS
(500–800 °C)2 to can be synthesized.
synthesize MoS2. The
Depending on the temperature for processing, both 2H and 3R phase of MoS
MoS2 nanoribbons can be 50 µm in length and are aligned in parallel arrays which are preferable for
2 can be synthesized.
deviceThe MoS2 nanoribbons
fabrication, as showncaninbeFigure
50 µ m in
4. length and are aligned in parallel arrays which are preferable
for device fabrication, as shown in Figure 4.

Figure 4. MoS
4. MoS 2 nanowires/nanoribbons synthesized from MoOx precursor [43].
Figure 2 nanowires/nanoribbons synthesized from MoOx precursor [43].

2.2.3. Chemical Vapor Deposition (CVD)

2.2.3. Chemical Vapor Deposition (CVD)
Among all the synthesis methods, CVD is the most compatible to existing semiconductor
Among all Typically,
technology. the synthesisit forms methods,
the film onCVD is the where
a substrate, most chemical
compatible to existing
reactions semiconductor
are involved in the
technology.
growth mechanism. The large-area growth of highly uniform MoS2 will enable the batch fabrication of in the
Typically, it forms the film on a substrate, where chemical reactions are involved
growth mechanism.
atomically The large-area
thin devices growth
and circuitry. of highly
Currently, uniform
most works MoS will solid
start 2with enable theprecursors
state batch fabrication
of
molybdenum,
of atomically thin such
devicesas MoO
and3 [46,47] or Mo
circuitry. [48]. If the most
Currently, Mo precursors are not
works start vaporized
with in theprecursors
solid state process, of
often the technique
molybdenum, is also called
such as MoO [46,47]sulfurization
or Mo [46–48].
[48]. If theTypical
Mo S precursorsare
precursors arenot
H2Svaporized
gas [49] or vaporized
in the process,
3
S [46–48,50]. It is argued that using MoCl5 precursors are easier to achieve monolayer MoS2 over large
often the technique is also called sulfurization [46–48]. Typical S precursors are H2 S gas [49] or
area [50]. Earlier, the MoS2 could be noncontinuous [47], which is not a big problem nowadays. The usual
vaporized S [46–48,50]. It is argued that using MoCl5 precursors are easier to achieve monolayer
growth temperatures are 700–1000 °C, and the inclusion of a metal catalyst such as Au is favorable for
MoS2 the
over large
film area
quality [50].
[49]. Earlier,
Typical the MoS
reactions 2 could
taking place inbethenoncontinuous [47], which is not a big problem
CVD are one of these:
◦
nowadays. The usual growth temperatures are 700–1000 C, and the inclusion of a metal catalyst such
MoO3+2H2S+H2=MoS2+3H2O (1)
as Au is favorable for the film quality [49]. Typical reactions taking place in the CVD are one of these:
8MoO3+24H2S=8MoS2+24H2O+S8 (2)
MoO316MoO
+ 2H23S+7S
+ 8H 2 = MoS
=16MoS 2 + 3H
2+24SO 2 2O (3) (1)

With plasma-enhanced chemical 8MoO 3 + 24H

vapor 2 S = 8MoS
deposition 2 + 24H
(PECVD), O+S8 temperature of MoS2 can be (2)
the 2growth
lowered to 150–300 °C, making it possible to directly deposit MoS2 even on plastic substrates [51].
16MoO + 7S = 16MoS2 + 24SO2 precursors are used. It is used in (3)
Metal-organic CVD is a special case 3of CVD8 where organometallic
the modern
With semiconductor
plasma-enhanced industryvapor
chemical to produce single crystal
deposition expitaxial
(PECVD), films. Recently,
the growth a few reports
temperature of MoS2 can
have appeared on the ◦ application of this method in the growth of MoS2 thin films [49,52–54]. Kang et al.
be lowered to 150–300 C, making it possible to directly deposit MoS2 even on plastic substrates [51].
[52] have grown MoS2 and WS2 on 4-inch oxidized silicon wafers by MOCVD. The MoS2 is grown with
Metal-organic CVD is a special case of CVD where organometallic precursors are used. It is
gaseous precursors of Mo(CO)6 (boiling point 156 °C) and (C2H5)2S. At 550 °C, monolayer MoS2 with
used in the
full modernofsemiconductor
coverage industry
the substrate (typically SiOto produce single crystal expitaxial films. Recently, a few
2/Si and fused silica) is deposited for t0~26 h. Figure 5a
reportsshows
have scanning
appearedelectron
on themicroscopy
application(SEM)
of thisimages
method in the
of the growth
samples, of MoS2 thinthe
demonstrating films [49,52–54].
effect of
Kang et al. [52]
adding H2 have
in the grown MoS2Itand
gas mixture. WS2 that
is argued on 4-inch oxidized
H2 enhances silicon wafersofby(CMOCVD.
the decomposition The MoS2 is
2H5)2S (increasing

grownnucleation
with gaseousdue to hydrogenolysis)
precursors and etches
of Mo(CO) MoS2 point
6 (boiling 156 ◦ C)
(preventing intergrain
and (C2connection) [52].◦ C,
H5 )2 S. At 550 It seems
monolayer
that a low H 2 rate is beneficial for growing continuous monolayer MoS2. Nevertheless, H2 is
MoS2 with full coverage of the substrate (typically SiO2 /Si and fused silica) is deposited for t0 ~26 h.
necessary for removing the carbonaceous species generated during the MOCVD. Therefore, the H2
Figure 5a shows scanning electron microscopy (SEM) images of the samples, demonstrating the
flow should be optimized. To have successful growth, dehydrating the growth environment is also
effect of adding H2 in the gas mixture. It is argued that H2 enhances the decomposition of (C2 H5 )2 S
necessary. Figure 5b indicates that the growth mode is layer-by-layer under this specific condition.
(increasing nucleation due to hydrogenolysis) and etches MoS2 (preventing intergrain connection) [52].
It seems that a low H2 rate is beneficial for growing continuous monolayer MoS2 . Nevertheless, H2 is
Crystals 2017, 7, 198 6 of 11

necessary for removing the carbonaceous species generated during the MOCVD. Therefore, the H2
flow should be optimized. To have successful growth, dehydrating the growth environment is also
necessary. Figure 5b indicates that the growth mode is layer-by-layer under this specific condition.
When t <Crystals
t0 there is almost no nucleation of the second MoS2 layer, which takes place mainly
2017, 7, 198 6 of 10
at the
grain boundaries of the first layer when t > t0 . Figure 5c shows a top gated (V TG ) MoS2 transistor with
Whenmobility
a field-effect t < t0 thereofis29
almost V−nucleation
cm2 no 1 s−1 andoftransconductance
the second MoS2 layer, which takes
2 µSµm, place mainly
determined fromat the
the transfer
grain boundaries of the first layer when t > t0. Figure 5c shows a top gated (VTG) MoS2 transistor with
properties. The current saturation occurs at relatively low V SD (see the inset). These features compete
a field-effect mobility of 29 cm2 V−1 s−1 and transconductance 2 µSµm, determined from the transfer
well withproperties.
the-state-of-the-art MoS2 transistors.
The current saturation Figure 5d–f
occurs at relatively low Vdemonstrates the optical absorption, Raman
SD (see the inset). These features compete
and photoluminescence spectra measured
well with the-state-of-the-art from theFigure
MoS2 transistors. MOCVD 5d–fgrown MoS2 (and
demonstrates WS2 ) absorption,
the optical films, respectively,
where the features
Raman agree well with the
and photoluminescence characteristics
spectra measured from of the
exfoliated
MOCVD monolayer
grown MoS2 counterparts
(and WS2) films,(denoted
respectively, where the features agree well with the characteristics of exfoliated monolayer
by diamonds).
counterparts (denoted by diamonds).

c
MoS2
MoS2 WS2
WS2
MoS2

WS2

(a) Grain
Figure 5.Figure size evolution
5. (a) Grain of of
size evolution monolayer MoS
monolayer MoS 2 as
2 as a function
a function of H2 of H2From
flow. flow.leftFrom left
to right, to right, 5,
5, 20
andsccm
200 sccm
H2 .H(b)
2. (b) Optical images
images ofof
MoS 2 films as a function of growth time. t0 is the optimal time
20 and 200 Optical MoS 2 films as a function of growth time. t0 is the optimal
for full monolayer coverage (~26 h). (c) Transfer and output properties of the field-effect transistor
time for full monolayer coverage (~26 h). (c) Transfer and output properties of the field-effect transistor
fabricated in the MOCVD grown MoS2 with top gate configuration. σ□ denotes sheet conductance.
fabricated in the MOCVD grown MoS2 with top gate configuration. σ denotes sheet conductance.
Scale bar: 10 µm. (d)–(f) Optical absorption, Raman and normalized photoluminescence spectra of
Scale bar:as-grown
10 µm.monolayer
(d–f) Optical absorption,
MoS2 (red) Ramanfilms.
and WS2 (orange) andThe normalized photoluminescence
peak positions in (d)–(f) are consistentspectra of
as-grownwithmonolayer MoS2(denoted
exfoliated flakes (red) and WS2 (orange)
by diamonds) [52]. films. The peak positions in (d–f) are consistent
with exfoliated flakes (denoted by diamonds) [52].
At this stage, the material quality in [53] is still too low to be competitive. The large-area
deposition of monolayer MoS2 as well as other TMDs with spatial homogeneity and high
At this stage, theis material
performance qualityMoS
still challenging. in [53] is still
2 films today too
arelow to be competitive.
polycrystalline with the The
grainlarge-area deposition
size typically
of monolayer MoS2 as well as other TMDs with spatial homogeneity and high performance is still
ranging from 1 to 10 micrometers. This notwithstanding, the MOCVD synthesis of 2D
semiconductors
challenging. MoS2 filmsindeed opensare
today a pathway towards future
polycrystalline withexciting nanoelectronic
the grain materials.
size typically The most
ranging from 1 to
important reason for this is that, in MOCVD, ultrapure gaseous precursors are injected into the
10 micrometers. This notwithstanding, the MOCVD synthesis of 2D semiconductors indeed opens
reactor and finely dosed to deposit a very thin layer of atoms onto the substrate. Even if a solid or
a pathway towards
liquid future
precursor exciting
is used, it will nanoelectronic
be vaporized in situ materials. The most
in the chamber important
[53]. Unlike reason
solid and for this is
liquid
that, in MOCVD,
precursors,ultrapure gaseous precursors
here the building-blocks for growing are the
injected
film are into thefiner,
much reactor and finely
naturally leadingdosed to deposit
to better
a very thin layer of atoms onto the substrate. Even if a solid or liquid precursor is used, it will be
vaporized in situ in the chamber [53]. Unlike solid and liquid precursors, here the building-blocks for
Crystals 2017, 7, 198 7 of 11

growing the film are much finer, naturally leading to better quality and controllability. The heated
metalorganic precursor molecules decompose via pyrolysis, leaving the atoms on the substrate. The
atoms bond to the surface, and an ultrathin MoS2 layer is grown.
Crystals 2017, 7, 198 7 of 10
Based on this argument, one can easily think of another promising synthesis method: ALD [55],
whichquality
can beand seencontrollability.
as a subclassThe of heated
CVD. In ALD, the film
metalorganic is grown
precursor by exposing
molecules decompose theviasubstrate
pyrolysis, surface
to alternating
leaving the gas precursors.
atoms In contrast
on the substrate. The atoms to ordinary
bond to the CVD, theand
surface, precursors
an ultrathinare
MoSnever
2 layersimultaneously
is grown.
present inBased on this argument,
the chamber. onethey
Instead, can easily think of another
are introduced as promising
sequentialsynthesis method: ALD [55],pulses,
and non-overlapping
whichby
separated canpurges
be seenin as between.
a subclass of InCVD.
eachInpulse,
ALD, the film is grown
molecules reactbywith
exposing the substrate
the surface in a surface
self-limiting
to alternating gas precursors. In contrast to ordinary CVD, the precursors are never simultaneously
way. Hence, it is possible to grow materials with high-thickness precision (layer by layer). Indeed,
present in the chamber. Instead, they are introduced as sequential and non-overlapping pulses,
very recently, people have used ALD to grow MoS2 , such as in [56]. Using MoCl5 (vaporized) and
separated by purges in between. In each pulse, molecules react with the surface in a self-limiting
H2 S precursors,
way. Hence,monolayer
it is possibletotofew-layer
grow materials MoS2with on large SiO2 /Si precision
high-thickness or quartz(layer
substrates
by layer).is obtained
Indeed, [56].
In thevery
photos of two 150 mm quartz wafers before and after the ALD, the
recently, people have used ALD to grow MoS2, such as in [56]. Using MoCl5 (vaporized) and substrate changes to dark
yellowHuniformly (~2 layers of MoS
2S precursors, monolayer to few-layer 2 ) [56]. MoS2 on large SiO2/Si or quartz substrates is obtained [56].lead to
It is found that photoresist residues on the surface
In the photos of two 150 mm quartz
more nucleation sites for MoS2 , but this mechanism wafers before and after the
remains toALD, the substrate
be confirmed. changes
Figure to darkRaman
6a plots
yellow uniformly (~2 layers of MoS 2) [56].1It is found that photoresist residues on the surface lead to
signals for 50 cycle ALD MoS2 , where the E 2g and A1g characteristic peaks are sharper and higher for
475 ◦ Cmore nucleation sites for MoS2, but this mechanism remains to be confirmed. Figure 6a plots Raman
deposition temperature, indicating its higher material quality. After the ALD, some samples are
signals for 50 cycle ALD MoS2, where the E12g and A1g characteristic peaks are sharper and higher for
annealed in a sulfur environment (H2 S or S atmosphere). Figure 6b shows that after sulfur annealing
475 °C deposition temperature, indicating its higher material quality. After the ALD, some samples
at increasingly
are annealed highintemperature, the characteristic
a sulfur environment (H2S or S peaks get narrower,
atmosphere). Figure 6b stronger
shows thatand after
moresulfur
symmetric.
After annealing ◦ 1
annealing atatincreasingly
920 C, thehigh fulltemperature,
width at half themaximum of the
characteristic E get
peaks 2g peak is close
narrower, to that
stronger andofmore
exfoliated
MoS2 symmetric.
monolayerAfter cm−1 vs. at
(4.2 annealing 3.7920
cm°C,−1 ). By analyzing the separation ∆ between
the full width at half maximum of the E12g peakEis1 2g andtoAthat
close 1g peaks,
of exfoliated MoS monolayer (4.2 cm −1 vs. 3.7 cm−1). By analyzing the separation Δ between E12g and
one can tentatively determine the number of layers in MoS2 films [56]. In Figure 6c, the sample grown
2

at 475A◦1gC peaks,
and annealed at 920 ◦ Cdetermine
one can tentatively seems tothe be number of layers inFuture
1–2 monolayers. MoS2 films [56]. In measurements
electronic Figure 6c, the are
sample grown at 475 °C
needed to further examine the film quality.and annealed at 920 °C seems to be 1–2 monolayers. Future electronic
measurements are needed to further examine the film quality.

(a)

(b)

(c)

(a)Raman
Figure 6. (a)
Figure Raman spectroscopy
spectroscopy measurements
measurements of ALDof ALD
MoS MoS
2 at 375 or2 475 °C, where
at 375 or 475the◦ C, where
latter showsthe latter
higher
quality.higher
shows (b) Raman spectra
quality. of 475 °C
(b) Raman deposited
spectra of 475 ◦
MoS2Cfilms (some are
deposited MoS post annealed in are
sulfur environment),
2 films (some post annealed in
sulfur 920 °C annealingwhere
where environment), leads to the◦ C
920 best quality. The
annealing curve
leads tofor
thebulk
bestMoS 2 is for The
quality. reference.
curve(c)for
E12g to AMoS
bulk 1g peakis
2
separation Δ plotted against the cycle number in ALD. Δ~19 cm −1 tentatively indicates MoS2 monolayer,
for reference. (c) E1 2g to A1g peak separation ∆ plotted against the cycle number in ALD. ∆~19 cm−1
whereas bulk (>5 layers) material has Δ~25 cm−1 [56].
tentatively indicates MoS2 monolayer, whereas bulk (>5 layers) material has ∆~25 cm−1 [56].
Crystals 2017, 7, 198 8 of 11

3. Conclusions
In this paper, we have reviewed the synthesis methods of MoS2 in terms of top-down and
bottom-up approaches. Micromechanical exfoliation offers the highest material quality but is limited
by the yield so it is mainly for basic research, whereas liquid phase exfoliation and solution chemical
process are of low cost, with decent material quality and suitable for large-scale industrial production.
MoS2 thin films aiming for high-end electronic applications are produced by CVD. In this review, we
have put a special emphasis on the MOCVD and ALD methods, because they are more sophisticated
technology with gas phase precursors and will most likely be the dominant techniques in producing
MoS2 films oriented towards real electronic device applications in the future. In most cases the
MoS2 films are transfer-free, which is vital for industrial applications that require a high process
controllability and reproducibility [57]. At the moment, production of MoS2 as a high quality electronic
material is still challenging. This notwithstanding, most of the reviewed processes can be extended to
other 2D materials (with some modification), and with future technological advances, the successful
production of advanced 2D nanoelectronic materials can be envisioned.

Acknowledgments: We would like to thank National Natural Science Foundation of China (11674016), National
key R & D program (2017YFB0403100), Beijing Natural Science Foundation (4152003), Beijing Municipal
Commission of Education (PXM2016_014204_500018), and Swedish Foundation for International Cooperation in
Research and Higher Education (CH2015-6202).
Author Contributions: J. Sun, X. Li and Y. Fu wrote the paper, led the discussion and summarized the literature;
W. Guo, M. Zhao, C. Xu and J. Deng participated in the discussion; X. Fan and Y. Dong helped to summarize
the literature.
Conflicts of Interest: The authors declare no conflict of interest.

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