Subbaiah Et Al-2016-Advanced Functional Materials

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FEATURE ARTICLE
Atomically Thin MoS2: A Versatile Nongraphene

2D Material
Y. P. Venkata Subbaiah, K. J. Saji, and A. Tiwari*
Unlike zero-band gap graphene (semi-

Two-dimensional inorganic materials are emerging as a premiere class of metal),[8] and large band gap hBN (insu-
materials for fabricating modern electronic devices. The interest in 2D layered lator),[9] the 2D transition metal dichalco-
transition metal dichalcogenides is especially high. Particularly, 2D MoS2 is genides (sulfides and selenides) have band
being heavily researched due to its novel functionalities and its suitability gaps comparable to conventional Si or
GaAs, and thus present a tantalizing pros-
for a wide range of electronic and optoelectronic applications. In this article,
pect of scaling all semiconductor science
the progress in mono/few layer(s) MoS2 research is reviewed by focusing and technology down to a truly atomic
primarily on the layer dependent evolution of crystal, phonon, and elec- scale. Although these transition metal
tronic structure. The review includes extensive detail into the methodologies dichalcogenides (TMDCs) are quite well
adapted for single or few layer(s) MoS2 growth. Further, the review covers known for the past few decades for their
applications in solid state lubricants,[10]
the versatility of 2D MoS2 for a broad range of device applications. Recent
photovoltaic devices,[11,12] and recharge-
advancements in the field of van der Waals heterostructures are also high- able batteries,[13] the recent methodolo-
lighted at the end of the review. gies and concepts evolved from graphene
research like exfoliation, transfer, and
manipulation of 2D materials have driven
1. Introduction interest toward the exploration of layered TMDCs. TMDCs pos-
sess hexagonal layers of transition metal atoms (M) sandwiched
2D materials constitute a unique class of materials in which between two layers of chalcogen atoms (X) with an MX2 stoi-
in-plane atomic bonding is much stronger than that along the chiometry. Depending on the different combinations of chal-
out-of-plane direction. These materials are usually artificially cogen (typically S, Se, or Te) and transition metal (mainly Mo
derived from layered van der Waals solids.[1] The crystal struc- and W) elements, several different kinds of TMDCs are pos-
ture of layered van der Waals solids is composed of one-atom- sible. Among the various combinations of TMDCs, MoS2 is the
thick or few-atom-polyhedral layers with tight covalent or ionic most promising 2D material as its elemental constituents are
bonding along two-dimensions (intralayer) and weak van der abundant, nontoxic, and amenable for easy mono/few layer(s)
Waals bonding along the third dimension (interlayer).[2] The synthesis when compared to their analogous selenides and
weak van der Waals bonding enables an easy splitting of the tellurides.
layered materials into individual monolayers. The 2D materials Despite graphene’s exceptionally high carrier mobility,[14]
differ in their phonon and electronic structure,[1,3] from their field-effect transistors (FETs) made from graphene cannot
bulk phases and exhibit unique and fascinating properties due effectively function as electronic switches due to the absence
to the quantum confinement of electrons and the absence of of an electronic band gap.[15,16] 2D MoS2 possesses a relatively
interlayer interactions. Graphene, a single layer of graphite high mobility up to 200 cm2 (V-s)−1 with a high on/off cur-
was the first real 2D material.[4,5] However, presently there are rent ratio of ≈108 at room temperature,[17–20] and has a layer
a large numbers of layered materials that can be cleaved or dependent band gap with a crossover from indirect (1.2 eV)
grown easily into 2D atomic planes,[6,7] including transition to direct (1.9 eV) at the bulk to monolayer transition, making
metal dichalcogenides. Figure 1 shows the current library of this a promising material for efficient electronic,[17,21] and
various 2D materials predicted beyond graphene.[6] The color optoelectronic devices.[22–24] The unique electronic band struc-
shading indicates 2D materials that are experimentally stable or ture and optical properties of monolayer MoS2 are suitable for
unstable in ambient conditions. a wide range of novel functional devices and hence has trig-
gered exhaustive research on this nongraphene material during
the last few years.[2,7,25–30] In this paper, we have done a com-
Dr. Y. P. Venkata Subbaiah, Dr. K. J. Saji, Prof. A. Tiwari prehensive review of the state-of-the-art research going on in
Nanostructured Materials Research Laboratory this area. The review primarily covers the intriguing changes
Department of Materials Science and Engineering occurring in the physical properties (crystal structure, layer
University of Utah dependent evolution of vibrational and electronic structure and
Salt Lake City, UT 84112, USA
E-mail: tiwari@eng.utah.edu
relevant optical properties) of MoS2 when one of the dimen-
sions (specifically the van der Waals dimension) is controlled,
DOI: 10.1002/adfm.201504202 followed by the description of various isolation or large-area
2046 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2016, 26, 2046–2069
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FEATURE ARTICLE
growth procedures. Finally, the review outlines many exciting
recent device developments in the field of 2D electronics and Venkata Subbaiah is presently
optoelectronics that include field-effect transistors (FETs), inte- working as a postdoctoral
grated circuits, logic devices, light emitting diodes, photovoltaic fellow at the University of Utah
devices, and van der Waals heterostructures. under Indo-US Raman post-
doctoral fellowship program
sponsored by the University
1.1. Crystal Structure of MoS2 Grants Commission of India.
He is on study leave from
In general, MX2 compounds can crystallize in more than one the Yogi Vemana University,
2D structures: the hexagonal (2H), octahedral (1T), and dis- Kadapa, India where he is
torted octahedral (1T´) structures.[31] Although all these phases an Assistant Professor of
consist of a metal atom (M) layer sandwiched between two Physics. He obtained his PhD
chalcogenide (X) layers, only 2H phase is semiconducting in Physics from Sri Venkateswara University, India in 2006.
and other phases are metallic. While the 2H phase is widely His Current research interests include thin film photo-
studied for electronic applications, the 1T´ phase is getting voltaic materials and 2D materials for next generation
renewed interest since it can exhibit large nonsaturating mag- optoelectronic devices.
neto resistance,[32] and spin–orbit coupling induced band gap
widening and quantum Spin Hall Effect.[33,34] In the case of
MoS2, the most commonly occurring crystal structure for Kachirayil J. Saji is presently
MoS2 is hexagonal (2H), which is thermodynamically more working as a postdoctoral
stable and has a layered structure with D6h point group sym- fellow at the University
metry.[35] Throughout this paper, we consider the 2H phase of Utah under Indo-US
of MoS2 unless otherwise specified. In its bulk form, crystal Raman post-doctoral fel-
structure of MoS2 consists of vertically stacked layers that are lowship program sponsored
linked via weak van der Waals forces between the layers, and by the University Grants
with strong in-plane covalent bonds between Mo and S atoms Commission of India. He
(Figure 2a).[17] Every single layer of MoS2 consists of a single is on study leave from the
sheet of Mo plane sandwiched between two planes of S atoms Government Victoria College,
and forms a 2D hexagonal crystal structure (Trigonal prismatic University of Calicut, India
arrangement) with a D3h point group symmetry (Figure 2b,c). where he is an Assistant
Each of the single layers has a thickness of ≈6.5 Å, with the Professor of Physics. He obtained his PhD in physics
distance between upper and lower sulfur atoms ≈3.2 Å.[36] from Cochin University of Science and Technology, India
The lattice constants of MoS2 monolayer are reported to be in 2009. His current research interests include elec-
≈3.22 Å with a covalent bond length of Mo-S of 2.43 Å and tronic and photovoltaic applications of two dimensional
the S–Mo–S bond angle of ≈80.56°.[29,35,37] The surface of materials.
2D-MoS2 is free from dangling bonds. A monolayer of MoS2
has an in-plane stiffness of 180 ± 60 Nm−1, corresponding to an
effective Young’s modulus of 270 ± 100 GPa, which is higher Ashutosh Tiwari is an
than that of steel (≈205 GPa) as well as of bulk MoS2 crystal Associate Professor
(≈240 GPa).[38,39] The breaking strength of monolayer MoS2 is of Materials Science
as high as 22 ± 4 GPa, which is between 6% and 11% of its & Engineering and
Young’s modulus[38] and hence the monolayer MoS2 can be the Director of the
deformed and bent to a curvature of radius 0.75 mm without Nanostructured Materials
losing its native properties.[39,40] This exceptional mechanical Research Laboratory at
maneuverability offers the use of MoS2 in flexible electronic the University of Utah.
and optoelectronic devices. He obtained his PhD in
experimental condensed
matter physics from Indian
1.2. Raman Active Vibrational Modes in MoS2 Institute of Technology in
2000. He joined the University of Utah in 2005 as an
Raman spectroscopy is a powerful tool to determine the crystal Assistant Professor of Materials Science & Engineering
phase and distinguish between bulk and mono/few layer(s) and was promoted to the rank of Associate Professor
present in layered van der Waals materials.[41–44] The group- with tenure in 2010. Tiwari has to date published more
theoretical analysis of the hexagonal Brillouin zone of single than 120 peer reviewed research articles (100+ in inter-
crystal 2H-MoS2 predicts that there are four first-order Raman national journals) and holds 7 US patents. His current
active modes, namely: E22g, E1g, E12g and A1g for wave numbers research interest is on spintronics and two dimensional
of ≈32, 286, 383, and 408 cm−1, respectively,[45–47] (Figure 3a,b). materials.
Additionally, there are two IR active modes: E21u (384 cm−1),
Adv. Funct. Mater. 2016, 26, 2046–2069 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 2047
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FEATURE ARTICLE
Figure 1. Existing library of 2D materials: monolayers proven as experimentally stable under ambient conditions (room temperature in air) are shaded
blue; those probably stable in air are shaded green; the 2D materials shaded in pink are unstable in air but may be stable in inert atmosphere. Gray
shading indicates 3D compounds that have been successfully exfoliated down to monolayers, but their oxides and hydroxides may exhibit stoichiometry
variations with their corresponding 3D counterparts. “Others” indicate 2D crystals—including borides, carbides, nitrides, and so on—have probably
been or can be isolated. Reproduced with permission.[6] Copyright 2013, Nature Publishing Group.
A2u (470 cm−1), and four silent modes: B22g (58 cm−1), E2u the presence of monolayer MoS2 with the value increasing con-
(287 cm−1), B1u (403 cm−1), and B12g (470 cm−1). The experi- sistently on increasing the number of layers in the film and
mental off-resonance,[46] and resonance Raman spectra have reaches ≈25 cm−1 for bulk MoS2,[3,51–58] (Figure 3c,d).
been extensively studied for bulk 2H-MoS2.[48,49] The E22g mode Several in-depth experimental studies have been per-
is caused by the lattice vibration of S Mo S layer against formed to understand the evolution of vibrational modes in
other adjacent layers, while the rest of the three modes belong MoS2 as the thickness of the specimen is reduced to a single
to intralayer vibrations. The E1g mode is forbidden in back-scat- monolayer.[43,49,52,59–62] When the layer number increases,
tering operation on a basal plane. E12g mode that results from the inter-layer van der Waals forces in MoS2 suppress
opposite vibration of two S atoms with respect to the Mo atom, vibrations, resulting in a higher restoring force acting on
and the A1g mode that is associated with the out-of-plane vibra- atoms,[52] and hence both A1g and E12g modes are expected to
tion of only S atoms in opposite directions are the most sensi- stiffen (blueshift). However, recent layer dependent Raman
tive modes to the number of layers present in the film.[50] The studies,[43,52] have shown that while the out-of-plane A1g mode
Raman shift difference between A1g and E12g modes (Δƒ) is a is consistent with the predicted stiffening with increasing
characteristic used to identify the number of layers present in layer number, the E12g mode softens (redshift) instead of the
MoS2 specimen. A Δƒ value between 18 and 20 cm−1 indicates expected blue-shift due to the dominant long-range Coulombic
Figure 2. a) 3D form of bulk MoS2, b,c) side and top views of 2D hexagonal layouts of single layer MoS2 (H-MoS2). a) Reproduced with permission.[17]
Copyright 2011, Nature Publishing group.
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FEATURE ARTICLE
Figure 3. a) Four active Raman modes of 2H- MoS2,[52] and b) Raman spectrum of 2H-MoS2.[47] c) Raman spectra of PLD grown MoS2 from bulk
(60 ML) to 1 ML. d) Wave numbers of E12g and A1g Raman modes and their difference (inset) as a function of number of monolayers.[55] a) Reproduced
with permission.[52] Copyright 2010, American Chemical Society. b) Reproduced with permission.[47] Copyright 2008, Chemistry Central Ltd. c,d) Repro-
duced with permission.[55] Copyright 2015, American Institute of Physics.
interlayer interactions in multilayer MoS2. It has also been constitutes an indirect band gap of 1.2 eV for bulk MoS2.[3,68]
observed that the full width at half maxima for the A1g mode The direct excitonic bands at K Brillouin point remain almost
increases on going from bulk to monolayer whereas the value unaffected as the number of layers in the film decreases, while
for the E12g mode remains unaffected.[43,52] In a recent report, the conduction band states between Γ and K and the valance
Terrones et al.[63] showed that in the case of monolayer MoS2 band states at the Γ point move apart and cause a widening in
films, due to the lack of inversion symmetry, the out-of-plane indirect excitonic transition that results in a direct band gap
and in-plane Raman modes should be represented by A1′ and for monolayer MoS2 (Figure 4b). Although, the direct excitonic
E′, respectively. However, in most of the earlier literature even states at the K point remain almost unchanged, there is a slight
for monolayer MoS2, peaks are indexed as A1g and E12g. increase in the direct band gap by about 0.05–0.1 eV.[67,69] In
conclusion, the bands at the Γ point and midway between Γ
and K points vary significantly on going from bulk to monolayer
1.3. Electronic Band Structure of MoS2 and establish a direct K–K band transition with a gap of ≈1.9 eV
for monolayer MoS2. The ultimate crossover from indirect to
Knowledge of electronic band structure is essential for under- direct band gap nature is quite intriguing and can be accounted
standing the electronic and optical processes in various elec- for by a combined effect of quantum confinement, long range
tronic and optoelectronic devices. The electronic band diagram Coulombic effects, and a change in the hybridization between
of graphene has a linear energy dispersion around the K point pz orbitals in S atoms and d-orbitals in Mo atoms.[3,35,51,70]
and exhibits a zero band gap.[64–66] The gapless electronic band Density functional theory (DFT) calculations showed that as
structure of graphene makes it unsuitable for fabricating effi- the Mo layer is sandwiched between two S layers, the conduc-
cient FETs. The electronic band structure of bulk and monolayer tion band states of d orbitals in Mo atoms at the K point are
MoS2 calculated from first principles is shown in Figure 4a, relatively unaffected by interlayer coupling; however, the states
which indicates a parabolic dispersion.[51,67] The valence band near the Γ-point, are severely affected due to combinations of
maximum (VBM) centered at the Γ point and the conduction the antibonding pz orbitals in S atoms and the d orbitals in Mo
band minimum (CBM) located midway in the Γ–K direction atoms.[51,69]
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Figure 4. a) Illustration of band structure for bulk and monolayer MoS2. Reproduced with permission.[67] Copyright 2011, American Physical Society.
b) Crossover from indirect to direct K → K transition from bulk to monolayer. b) Reproduced with permission.[51] Copyright 2010, American Chemical
Society. c) Normalized photoluminescence spectra of MoS2 with one monolayer to six monolayers showing the exciton peaks A and B along with
indirect transition. Reproduced with permission.[3] Copyright 2010, American Physical Society. d) Enhanced PL spectrum of single layer MoS2 under
ionic gated liquid. Reproduced with permission.[79] Copyright 2014, Springer Science and Business Media.
1.4. Photoluminescence Characteristics of MoS2 binding energy also changes drastically showing an increase
from ≈0.1 eV in bulk to 1.1 eV in monolayer samples.[71] Bulk
As discussed in Section 1.3, the band gap of MoS2 changes MoS2 is an indirect band gap semiconductor and produces
from indirect to direct band gap during the transition an insignificant photoluminescence. However, a changeover
from bulk to monolayer. During this transition, the exciton to a direct band gap material in its monolayer form, yields
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a gigantic photoluminescence, about 104 times higher
FEATURE ARTICLE
single layer flakes of graphene using the same approach. The
than that of bulk.[22,24,51,72–75] Despite this, still the reported micromechanical cleavage involves, a fresh surface of a layered
values, lying between 10−5 and 10−6 for few-layer MoS2 sam- crystal being either rubbed against another substrate surface or
ples and up to 4 × 10–3 for monolayer MoS2 samples, are far pressed against the “scotch tape,” which leaves a combination
behind the near unity values expected for direct band gap of single or few layer flakes attached to the substrate or “scotch
semiconductors.[3] tape.” For synthesizing mono/few layer(s) MoS2, bulk MoS2
The photoluminescence spectra of MoS2 exhibits two exci- single crystal is pressed against an adhesive scotch tape and
tonic peaks denoted as A (≈1.9 eV) and B (≈2.05 eV) around subsequent repeated exfoliation leaves the flakes adhered to it,
the K zone[3,51] (Figure 4c). These peaks are shown to origi- which are then transferred to substrates.[3,17,22,49,51,52] As these
nate from the direct excitonic transitions at the K zone, with monolayers are highly transparent, the transferring substrate
the energy splitting (≈0.15 eV) resulting from the combined must be a thick (opaque) dielectric layer (usually 200–300 nm
effect of interlayer coupling and valence band spin–orbit of SiO2 on Si). The color contrast under optical microscope
coupling.[3,69] The photoluminescence of MoS2 is also quite sig- (Figure 5a) between the substrate and mono/few-layer helps
nificantly affected by the type of substrate, doping, and ionic to identify the formation of single/few layer MoS2.[17,38,51,52,78]
liquid gating. For example, Li et al.[76] demonstrated the effect Subsequent AFM height profile measurements (Figure 5b)
of substrate on photoluminescence of monolayer MoS2. They provide the information about the number of layers in the
showed that through the selection of different substrates, dif- specimen.[39,43,59,81] Although micromechanical exfoliation
ferent amounts of charges can be induced into the monolayer technique is quite simple and produces high quality flakes,
MoS2, that can in-turn modify the relative intensities of the the yield of this technique is extremely low and results in
charged exciton (trion),[77] and neutral exciton.[58,76,78] Mouri irregular shaped flakes with high percentage of few layers than
et al. showed that the solution-based chemical doping can perfect monolayer of MoS2. Gacem et al. proposed a modified
also be an effective route to alter the photoemission through micromechanical exfoliation technique with anodic bonding to
the adsorption of p-type and n-type dopants by switching produce high quality and larger size single-layer and few-layers
the recombination process between exciton and trions.[75] In 2D materials.[82]
another study, Li et al. showed that the magnitude of the pho- There are also some reports on layer by layer laser thin-
toluminescence can also be increased by using ionic liquid ning,[83] thermal annealing,[84] and plasma (Ar+) thinning,[85]
gating which passivates the surface states and traps charges of mechanically exfoliated MoS2 few layers to obtain high
that act as recombination centers.[79] Using this approach they yield of monolayer MoS2 samples with good shape control and
reported almost a 300% enhancement in the photolumines- improved lateral sizes. However, despite their success in con-
cence intensity (Figure 4d). trolling the thickness down to monolayer, prolonged exposure
to radiation in laser thinning and thermal thinning techniques
causes rougher morphology. Compared to laser and thermal
2. Methods of Synthesis thinning, the Ar+ plasma thinning has been shown to be a
more reliable technique, with much less surface roughness.[85]
There are two major synthesis routes, which have been readily
utilized for synthesizing MoS2 monolayers. The first one is
based on exfoliation techniques and usually results in very 2.1.2. Chemical Exfoliation
small area flakes. While, the second route is based on vapor
deposition techniques and can result in large area growth of Layered TMDCs can be prepared by chemical exfoliation tech-
monolayer MoS2. niques also known as liquid-phase exfoliation.[86,87] Liquid-
phase exfoliation, in general, involves the separation of layered
materials through intercalation or dispersion followed by son-
2.1. Exfoliation Techniques ication to yield single and few layer flakes.[86,88] Liquid-phase
exfoliation methods are convenient and result in materials big
Exfoliation is the most widely employed method for preparing enough to be usable in various thin film applications.[89] The
monolayer or few layer MoS2 samples. The fragile van der simplest lithium ion intercalation method uses the concept
Waals forces (40–70 meV),[2] across the interlayer allow easy of lithium ion insertion between the MoS2 layers to widen
isolation of layered materials into mono or few layer(s) using the gaps between the layers, often using n-butyllithium in
exfoliation techniques. There are two subclasses of exfoliation hexane as the lithium source. The subsequent addition of
techniques namely micromechanical exfoliation and chemical water removes the lithium, and a sonication process allows
exfoliation. the layers to separate and be retrievable.[90,91] Organic solvents
such as methanol, ethanol, and isopropyl alcohol as well as
rapid heating in vacuum at around 600 °C can also be used
2.1.1. Micromechanical Exfoliation instead of lithium intercalation to separate the layers of MoS2.
Although these liquid methods (both lithium intercalation as
In 1999, a micromechanical approach was used for the first well as organic solvents, etc.) are simple, they are rather time
time by Lu et al.[80] to obtain thin graphite sheets from the pat- consuming (taking up to 3 days), sensitive to environmental
terned highly oriented pyrolytic graphite. Later, in 2004, Novo- conditions, and either produce a low yield with incomplete
selov et al.[1,4] demonstrated the perfect isolation of truly 2D separation or result in structural deformations of the 2H-MoS2
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FEATURE ARTICLE
Figure 5. a) Optical and b) AFM height profile images of exfoliated few and monolayer MoS2.[52] c) Photograph of dispersion of MoS2 at different
centrifuging rates for size selection. d) Sample images of MoS2 flakes prepared with different sonication times of 23, 70, and 106 h and high-resolu-
tion TEM image of MoS2 showing hexagonal symmetry. e) TEM micrographs of size selected dispersions produced by centrifugation at 300 rpm.[94]
a,b) Reproduced with permission.[52] Copyright 2010, American Chemical Society. c–e) Reproduced with permission.[94] Copyright 2012, American
Chemical Society.
(hexagonal) to 1T-MoS2 (octahedral),[73,92] due to excess interca- enough for practical applications. A drastic enhancement in
lation of lithium ions. The high-yield production of single-layer the concentration of exfoliated MoS2 (around 40 mg mL−1) with
MoS2 using liquid exfoliation has been demonstrated by Zeng increased flake sizes up to 700 nm has recently been reported
et al.[92] using a controllable electrochemical lithiation process, by O’Neill et al.[94] using N-Methyl-2-pyrrolidone as the solvent
which is different compared to the conventional lithium inter- with a controlled sonication time between 23 and 60 h and a
calation process.[73] However, due to the nature of the complex centrifugation rate of 1500 rpm. The longer sonication times
electrochemical process, its scope is limited. A mixed sol- (60–140 h) caused a reduction in the flake sizes to 400–200 nm
vent strategy has been suggested by Zhou et al. using a low due to the sonication induced scission. These results demon-
boiling point solvent mixture of 45 vol% ethanol in water. They strate that controlled centrifugation coupled with sediment
obtained a yield of 0.018 ± 0.003 mg mL−1 for MoS2 nanosheets recycling can be an effective route to separate dispersed MoS2
(≈2–4 nm), which is ≈13 times higher than that with pure eth- nanosheets by size (Figure 5c–e). The color of the resultant
anol and 68 times higher than that with pure water.[93] More dispersions varies strongly with the final centrifugation rate,
recently, Coleman et al.[86,87] succeeded in obtaining suspended which can be used to confirm that the size of the nanosheets
flakes of various TMDCs, including MoS2, with a high yield has indeed changed.
(≈0.3–0.5 mg mL−1). They initially sonicated the MoS2 powder
in two different types of solvents with varying surface tensions:
(1) N-Methyl-2-pyrrolidone (NMP),[86] and (2) aqueous sur- 2.2. Vapor Deposition Techniques for Large Area
factant sodium cholate.[87] The resultant dispersions were cen- Growth of MoS2
trifuged and the supernatant was decanted. The results showed
a good stabilization and prevented the 2D nanosheets from Exfoliation techniques remain simple and reliable techniques
aggregating during the slow solvent evaporation. Furthermore, to demonstrate the concepts and features of 2D materials and
the use of organic/inorganic solvents avoids structural defor- devices for research. However, it is very important to develop
mations and is insensitive to environment, and may poten- large area growth methods to synthesize mono or few layer(s)
tially be scaled up to obtain large quantities in hybrid sheets. TMDCs in order to extend the applicability of 2D materials
An improvement of up to 0.8 mg mL−1 yield with sizes var- from flake scale to wafer scale. Vapor-based deposition tech-
ying from 50–700 nm has been reported by Yao et al.[88] using niques, both chemical vapor deposition as well as physical
aqueous sodium dodecyl sulfate solution as a surfactant in com- vapor deposition, have been explored recently for such purpose.
bination with ball milling and sonication. Despite solvent and
surfactant exfoliated MoS2 being efficient means for producing
higher concentrations of flakes, bilayer and few layer flakes are 2.2.1. Chemical Vapor Deposition
far more abundant than single layer flakes. Additionally, the
dispersed concentrations are still below 1 mg mL−1 with lateral The 2D MoS2 growth procedure by chemical vapor deposi-
flake sizes found to be around 200–400 nm, which are not large tion (CVD) normally involves either a single step vapor phase
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FEATURE ARTICLE
Figure 6. Schematic illustration of various approaches to chemical vapor deposition of 2D-MoS2 synthesis using a) single step MoO3 sulfuriza-
tion,[53] and b) two-step annealing of MoO3.[98] c) Thermal decomposition of (NH4)2MoS4,[109] and d) Gas phase (H2S) sulfurization of metallic Mo
precursor.[113] e) MoCl5 sulfurization,[54] and f) vapor-phase growth using MoS2 precursor.[23] a) Reproduced with permission.[53] Copyright 2012, Wiley-
VCH. b) Reproduced with permission.[98] Copyright 2012, Royal Society of Chemistry. c) Reproduced with permission.[109] 2012, American Chemical
Society. d) Reproduced with permission.[113] Copyright 2014, Royal Society of Chemistry. e) Reproduced with permission.[54] Copyright 2014, Wiley-VCH.
f) Reproduced with permission.[23] Copyright 2014, American Institute of Physics.
co-deposition of solid precursor and sulfur onto adjacent/top mounted on the top of the MoO3 boat and the chamber was
mounted insulating substrate at elevated temperatures,[53] or a heated to 650 °C in a nitrogen atmosphere (Figure 6a). Their
two-step process that involves precursor deposition on desired results demonstrated that the growth of MoS2 is very sensitive
substrate (mostly insulators or metals) followed by vapor to substrate pretreatment. Mann et al.[97] employed a CVD setup
phase sulfur annealing.[95,96] So far, the growth of MoS2 by analogous to that used by Lee et al.[53] for the growth of small
CVD technique has been explored using the following five dif- areas of MoS2 monolayers using MoO3 and sulfur powders as
ferent types of Mo sources: MoO3, ammonium thiomolybdate the Mo and sulfur sources, and found that heating the tube fur-
[(NH4)2MoS4], metallic Mo, MoCl5, and MoS2. nace for 3 min (till the sulfur melts) results in the best deposi-
Chemical Vapor Deposition Using MoO3 Precursor: Balendhran tion. Their transport measurements showed an n-type conduc-
et al.[95] were among the first few groups to demonstrate the tivity with a bit poor mobility of 0.26 cm2 (V-s)−1. Lin et al.[98]
growth of atomically thin MoS2 using codeposition of MoO3 proposed a modified method to synthesize wafer-scale MoS2
and sulfur onto quartz substrates at 750 °C. Codeposited films thin layers by using a two-step thermal annealing process.
were annealed in the excess of sulfur for 180 min at 830 °C to Initially, the ultrathin films of MoO3 were thermally depos-
achieve MoS2 layer. Lee et al. reported the CVD growth of large ited on c-plane sapphire substrates at the rate of 0.05 nm s−1
area monolayers of MoS2 on amorphous SiO2 substrate.[53] followed by a first anneal in a H/Ar environment at 500 °C for
Their experimental setup consisted of a reaction chamber 60 min followed by a second anneal in a sulfur environment
with two adjacent ceramic boats loaded with MoO3 powder at 1000 °C for 30 min. Their results showed that the two-step
and sulfur powder. The upside down SiO2/Si substrate was process is more suitable for obtaining higher carrier mobility
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FEATURE ARTICLE
than the one step direct sulfurization process (Figure 6b). In the hot zone while the sulfur powder was loaded onto another
a later study, Ji et al.[58] reported epitaxial growth of centimeter ceramic boat and placed up-wind in the low temperature zone
scale monolayer of MoS2 on nearly lattice matched mica sub- (≈113 °C). The resulting CVD grown MoS2 films showed
strates using low pressure chemical vapor deposition (LPCVD). resistivities of 1.46 × 104 to 2.86 × 104 Ω ⵧ–1 with mobilities
A slightly different approach was employed by Wang et al.,[99] ranging from 0.004 to 0.04 cm2 (V-s)−1 with a p-type behavior.
who used thermally evaporated MoO3 as the starting mate- Laskar et al.[112] successfully grew large area, single crystal
rial, which was then reduced in a sulfur vapor followed by the MoS2 films by sulfurization of e-beam evaporated Mo films
layer-by-layer sulfurization of the reduced MoO2 micro plates deposited on c-axis oriented sapphire substrates and found
before finally obtaining MoS2 flakes with a rhomboidal shape that the high temperature growth between 900 and 1100 °C
and a domain size of ≈10 µm. Many similar fabrication routes yields high quality, expitaxially oriented, single crystal MoS2
of MoO3 sulfurization have been adopted recently by various films. These films exhibited a high field effect mobility of 12
research groups for achieving large area growth of monolayer ± 2 cm2 (V-s)−1 with an n-type behavior. Recently, Lee et al.[113]
MoS2.[100–104] demonstrated a CVD method of sulfurization of e-beam evap-
Chemical Vapor Deposition Using Thermolysis of Ammonium orated Mo films using a gas phase sulfur precursor (H2S) to
Thiomolybdate: Thermolysis of ammonium thiomolybdates, realize wafer scale, uniform MoS2 films with absolute control
(NH4)2MoS4 has also been explored to synthesize over the number of layers (Figure 6d). The thickness of the
2H-MoS2.[105–108] For example, Liu et al.[109] reported the MoS2 film was controlled by varying the thickness of the metal
growth of large area, high quality MoS2 layers on sapphire and film. The electron beam evaporated Mo films were placed in a
SiO2/Si substrates by this technique. In their study the thermal tubular quartz chamber and then heated to 750 °C under argon
decomposition of (NH4)2MoS4 solution was performed by first flow (50 sccm). The injection of H2S/H2/Ar (1:5:50) reaction
annealing it in an Ar+H2 atmosphere at 500 °C under a pres- gas mixture over 15 min converted the Mo into a MoS2 film.
sure of 1 Torr for 60 min followed by a second annealing in During the deposition, the chamber pressure was maintained
an Ar+S atmosphere at 1000 °C under a pressure of 500 Torr at 3.1 × 10−1 Torr. The introduction of H2 was noted as an
for 30 min. Initially, 0.25 g of solid (NH4)2MoS4 was added to essential step to avoid the oxidation of predeposited metal film.
20 mL dimethylformamide (DMF) to form the ammonium Orofeo et al.[114] followed a slightly different approach that
thiomolybdate solution. The sapphire or SiO2/Si substrates involved the reaction of DC magnetron sputtered Mo film with
were dipped vertically into the ammonium thiomolybdate solu- a sulfur vapor (from the solid sulfur powder). Their method
tion to form an ultrathin film of (NH4)2MoS4. This process was successfully produced centimeter scale MoS2 sheets on MgO
followed by a two-step annealing as shown in Figure 6c to pro- substrates with grain sizes varying from 50–200 nm. Very
duce high quality, thin layers of MoS2. During the annealing recently, Ahn et al.[115] demonstrated a low-temperature syn-
process, the (NH4)2MoS4 films decomposed into NH3, H2S, thesis of large area, few layer MoS2 directly onto polyimide (PI)
and MoS3 before finally forming MoS2. The presence of H2 is substrates by starting with electron beam evaporated Mo using
essential during annealing in order to avoid oxidation, and it plasma enhanced chemical vapor deposition (PECVD) in the
was noticed that the direct annealing of (NH4)2MoS4 films in ambience of H2S. This was the first report of the direct deposi-
an inert atmosphere with sulfur did not produce high quality tion of wafer scale 2D MoS2 onto flexible substrates (at tem-
MoS2 films. peratures between 150 and 300 °C) without using a transfer
Shi et al.[110] employed an alternative approach based on method.[81,113] These films exhibited an average mobility of
reduced graphene oxide (rGO),[111] that could act as a good 3.7 cm2 (V-s)−1. The low temperature PECVD approach opens
template for MoS2 nanoflakes. Their method used (NH4)2MoS4 a new pathway for the synthesis of 2D materials directly onto
solution together with rGO dissolved in an organic solution. plastic substrates, and can be extended for the fabrication of
They demonstrated the epitaxial synthesis of MoS2 nanoflakes transparent flexible semiconductor devices with high quality
over graphene covered Cu foil at a relatively low temperature and uniformity.
of 400 °C. Their idea was based on the fact that the planar sur- Chemical Vapor Deposition Using MoCl5 Precursor: Yu et al.[116]
face of CVD grown graphene (CVD-G) is free from dangling reported the growth of monolayer and bilayer MoS2 films on
bonds. This coupled with its weak van der Waals forces could SiO2, sapphire, and graphite substrates using MoCl5 and sulfur
play an important role for achieving a better growth of MoS2. precursors at relatively high temperatures (>800 °C). They
A low dose of (NH4)2MoS4 with the solvent lead to the island showed that the number of layers in the resulting MoS2 films
growth of MoS2 on the graphene and, as the dose of precursor can be precisely controlled by modifying the amount of MoCl5.
increased, the isolated MoS2 islands packed into continuous The as-grown films showed an n-type behavior with a field
MoS2 nanosheets through coalescence. effect mobility varying in the range 0.003–0.3 cm2 (V-s)−1. More
Chemical Vapor Deposition Using Mo Precursor: Zhan et al.[96] recently, McCreary et al.[54] demonstrated the synthesis of large
employed a different CVD route based on a metallic Mo pre- area monolayer heterostructures comprising of MoS2/graphene
cursor followed by vapor phase sulfurization to achieve large on SiO2/Si substrate using MoCl5 and S precursors (Figure 6e).
area growth of single or few layer(s) MoS2 films on SiO2 sub- In that study, the graphene was grown on Cu foil and then
strate. Initially, a thin layer of Mo (≈1–5 nm) was predeposited transferred onto the SiO2/Si substrate. The schematic diagram
using e-beam evaporation onto SiO2 followed by sulfurization of their experimental set up is depicted in Figure 6e.
under a N2 atmosphere at 750 °C for 10 min. The experimental Chemical Vapor Deposition Using MoS2 Precursor: Wu et al.[117]
setup consisted of a two-zone reaction quartz tube, in which used MoS2 precursor to obtain high optical quality monolayer
Mo coated films were placed into ceramic boats at the center of MoS2 on a variety of insulating substrates (SiO2, sapphire, and
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FEATURE ARTICLE
Figure 7. Schematic diagram of preparation of MoS2 PLD target followed by pulsed laser deposition and photograph of centimeter scale monolayer,
bilayer, trilayer, and few layer MoS2 nanosheets on sapphire (numbers indicate number of monolayers).
glass). The growth was carried out in a horizontal quartz tube and a laser energy density of 2 J cm−2. Later, Loh et al.[122]
furnace with MoS2 powder as the source placed at the center of studied the growth mechanism of few layer MoS2 on variety of
the furnace which was heated to 900 °C with Ar as the carrier metal substrates (Cu, Ni, Al, Ag) using PLD and demonstrated
gas. Substrates were kept at ≈650 °C and were placed far from that the highly crystalline few layer MoS2 can be grown on Ag
the center of the tube. The triangular shaped islands of MoS2 substrates using a laser energy density of 5 J cm−2, but not on
monolayers with side lengths up to ≈25 µm were obtained by other metallic substrates due to either excessively strong or poor
this method. A slightly modified method was proposed by Luo ad-layer substrate interactions. However, the growth of sem-
et al.[23] which involved the direct decomposition of MoS2 at icrystalline few layers MoS2 was achieved on Al substrates by
900 °C (Figure 6f). They successfully grew large areas of double adjusting a longer deposition time coupled with very high laser
layer MoS2 on SiO2 substrates and found that the films were energy density of 20 J cm−2, suggesting that the substrate inter-
highly sensitive to photo illumination. actions can be screened out by increasing the supply of Mo and
Although CVD is a promising technique and is capable of S atoms at the surface by using large laser energies. In a subse-
producing large area MoS2 films, the CVD grown MoS2 mono/ quent study, Serrao et al.[57] reported PLD grown highly crystal-
few layer(s) are still poor in quality and their carrier mobilities line MoS2 thin films consisting of monolayers on 5 × 5 mm2
are significantly low,[53,96,109] compared to exfoliated flakes due substrates of Al2O3 (0001), GaN (0001), and SiC-6H (0001). Sim-
to the high temperature growth processes that induce various ilarly, RHEED-assisted pulsed laser deposition of layered MoS2
kinds of defects in the final sample.[103,118–120] Therefore, there on c-sapphire has also been demonstrated recently.[56] In a more
is a need for developing alternative synthesis methods capable recent study, Siegel et al. reported the PLD growth of centimeter
of producing high quality and large area MoS2 thin films with a scale, atomically thin MoS2 thin films.[55] They demonstrated that
good control over the number of layers. the number of monolayers in the MoS2 film can be precisely con-
trolled down to a single monolayer (ML) by just controlling the
number of incident laser pulses. The schematic process starting
2.2.2. Physical Vapor Deposition from MoS2 powder to the growth of centimeter scale 1 mon-
olayer (ML), 2 ML, 3 ML, 4 ML, 10 ML, and 60 ML is shown in
In a recent study, Late et al.[121] employed a relatively less Figure 7.
explored physical vapor deposition technique, specifically pulsed
laser deposition (PLD), for producing nearly stoichiometric
nanostructures of MoS2 on a tungsten tip as well as on Si sub- 3. Device Applications
strates. Their method involved the laser ablation of a MoS2 target
prepared from MoS2 powder. The deposition was carried out at One of the main benefits of MoS2 compared to graphene is its
700 °C under Ar atmosphere with a pressure of 1 × 10−2 mbar nonzero band gap. Specifically, graphene has a zero band gap;
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FEATURE ARTICLE
it is semimetallic in nature, which means even though it has top gate length, source to gate, and gate to drain spacings were
a very high mobility, transistors made from it cannot be effec- 500 nm (Figure 8a,b). The top gated MoS2 FET demonstrated
tively turned off. MoS2, however, has a nonzero band gap and significant improvement in the mobility (>200 cm2 (V-s)−1)
acts as a semiconductor, which means it is a suitable candidate with a drain current on/off ratio of 108 and a subthreshold
for applications in electronic and logic devices as its conduc- swing (SS) of 74 mV dec−1 (Figure 8c). The device showed a
tivity can be modulated. Additionally, although MoS2 exhibits maximum on-current of 10 µA (2.5 µA µm−1) and a transcon-
an indirect band gap in the bulk phase, when its thickness is ductance of 4 µS (1 µS µm−1). Yoon et al.[124] performed subse-
reduced to a single monolayer its band gap becomes direct. quent simulation studies to estimate the ultimate performance
This implies that monolayer MoS2 can also find application in limit of top gated MoS2 monolayer transistors using HfO2 as
optoelectronic devices. Furthermore, due to the 2D nature of the top gate dielectric material (Lg = 15 nm and tgox = 2.8 nm),
MoS2, electrostatic control of the material also becomes viable analogous to the previous experimental device. The simula-
that can allow for the creation of low power electronic devices tion results (Figure 8d) predicted a high on-off ratio (>1010)
and short channel FETs. This section gives an overview of the and sharp switching (SS ≤ 60 mV dec−1) with excellent short
progress made in electronic and optoelectronic device tech- channel behavior (drain induced barrier lowering as low as
nology using mono/few layer MoS2 films. 10 mV V−1).
In a subsequent experimental study, Lembke and Kis dem-
onstrated a high performance transistor with a mobility of
3.1. Field Effect Transistors Based on MoS2 1090 cm2 (V-s)−1 at a drain voltage of 20 mV,[125] which is the
highest mobility reported so far for monolayer MoS2 tran-
The most fundamental component of modern electronic sistors. This high value was understood to be due to full-
devices is the field effect transistor (FET). Steady advances and channel gating. Furthermore, their transistors exhibited almost
progress in semiconductor manufacturing technology, particu- two orders of magnitude enhancement in the on-current
larly in lithography, have allowed the reduction of transistor (250 µA µm−1) compared to previous reports. The high on-
sizes to just a few nanometers. The latest breakthrough of current in these transistors can support large current densities,
Intel’s 3D device processors has a 14 nm node in silicon-based close to 5 × 107 A cm−2, which is 50 times higher than the crit-
metal-oxide-semiconductor field effect transistors (MOSFETs). ical current density of copper. This is understood to be due to
Despite the many desirable advantages like cost reduction, much stronger intralayer Mo-S covalent bonds in 2D MoS2 than
fast switching, and lower power consumption associated with metallic bonds. Besides, its success for digital electronics appli-
the size reduction of transistors, scaling much further beyond cations,[126–128] the above results demonstrate that monolayer
14 nm has limitations due to quantum mechanical tunneling MoS2 could also be an interesting candidate for analog circuit
between the drain and the source of the transistors as well applications as it could provide better power gains and support
as due to joule heating.[25] In order to make nanometer-sized larger current densities as well. More recently, Krasnozhon
devices that are free from short-channel effects, it is necessary et al.[129] tested the operational radio frequency (RF) perfor-
to use thinner gate oxides as well as thinner channel materials. mance of top-gated monolayer, bilayer, and trilayer MoS2 tran-
This can be easily understood by looking into the Poisson equa- sistors in the gigahertz range of frequencies, where commercial
tion modeled for natural length[123] devices are operated. The results of these MoS2 RF-FETs show
an intrinsic transconductance higher than 50 µS µm−1, a satura-
λ = ε ch dch dox /ε ox tion of drain-source current, and a voltage gain larger than 1 up
to 5 GHz frequency. Trilayer MoS2 FETs have shown a cut off
In the above equation, ε ch and ε ox are dielectric constants of frequency as high as 6 GHz. Although the performance of the
the channel material and the gate oxide, whereas dch and dox RF-MoS2 FETs are rather limited, further modification in device
correspond to the thicknesses of channel and the oxide layer, geometry and material processing could lead to the realization
respectively. The 2D van der Waals materials are considered as of full potential of 2D semiconductors for low-cost and flexible,
an excellent choice for channel material and it is expected that high-frequency analog current and voltage amplifiers as well
by using these materials, it will be possible to continue minia- as high-frequency logic circuits. Considering the potential of
turization much beyond the physical limits of current silicon- single layer MoS2 transistors for forming short channel FETs,
based technology.[25,27] there have been many studies where various different kinds
The first mechanically exfoliated MoS2-based FET was of gate dielectrics such as Al2O3,[130,131] ionic liquid,[132–134] and
reported by Novoselov et al. in 2005,[1] soon after their pio- polymer gated dielectrics[135,136] were utilized. The use of Al2O3
neering work on graphene. They found, however, that the dielectric in a bottom gate multilayer MoS2 FET device gave
material displayed a low mobility of ≈3 cm2 (V-s)−1 and a rel- rise to a mobility of 100 cm2 (V-s)−1,[137] that was significantly
atively low on/off ratio. The issue of lower mobility in single elevated to 170 cm2 (V-s)−1 and 517 cm2 (V-s)−1 for top-gated and
layer MoS2 transistors was addressed by Radisavljevic et al.[17] dual-gated single layer MoS2 FET devices, respectively.
by using a high-k dielectric material, HfO2. To date, this report A common characteristic of charge carriers in 2D materials
is treated as the first successful demonstration of a switchable is their low effective mass, which helps fast charge transport
transistor using single layer MoS2. In their work, an exfoliated across the material and hence the high field effect mobility in
MoS2 monolayer was transferred onto a silicon substrate cov- FETs. However, low effective mass also implies low density of
ered with 270 nm thick SiO2. HfO2 was utilized as the top gate states near the band edges, which leads to high contact resist-
oxide. The measured top gate width was reported as 4 µm and ance at 2D material-metal interfaces because of the reduced
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FEATURE ARTICLE
Figure 8. a) Optical image of a device composed of two field effect transistors connected in series with three gold contacts serving as source and drain
for two FETs. b) Cross-sectional view of the single layer MoS2 FET with electrical contacts and c) transfer characteristics of top gate single layer MoS2
FET. Drain current on/off ratio varied from 106 to 108 by varying Vds from 10 to 500 mV.[17] d) Simulated transfer characteristics of a monolayer MoS2
in both log and linear scales.[124] e) Schematic illustration of multilayer MoS2 FET with ionic liquid gate and f) temperature dependence of field-effect
mobility in ionic liquid gated MoS2 FET.[133] a–c) Reproduced with permission.[17] Copyright 2011, Nature Publishing Group. d) Reproduced with permis-
sion.[124] Copyright 2011, American Chemical Society. e,f) Reproduced with permission.[133] Copyright 2013, American Chemical Society.
availability of states for effective charge injection.[138] None of decreased from 180 K to 77 K (Figure 8f). Moreover, the use
the metal-MoS2 interfaces are completely Ohmic and hence of an ionic liquid as the dielectric material resulted in ambi-
the formation of Schottky barriers at the metal/channel inter- polar operation in contrast to the commonly observed n-type
face causes substantial reduction in the device mobility due behavior.[132,146]
to high contact resistance.[20,139] There have been proposed Even though the use of an ionic liquid gate in MoS2 FETs
methods, either using a low work function material,[140–142] or is highly successful, the instability of the liquid body causes a
surface doping in the contact region via chemical/molecular hindrance for all practical purposes. This critical problem asso-
doping,[143–145] in order to achieve highly transparent tunneling ciated with liquids has recently been resolved by gelation. An
contacts. Alternatively, Perera et al.[133] introduced electrostatic ionic gel is capable of combining the flexibility of an organic
doping through use of an ionic liquid (Figure 8e) as the top polymer dielectric with the high performance of an ionic
gate to achieve low resistance MoS2/metal tunneling contacts. liquid.[40] In more recent studies, the use of polymer-based
This study demonstrated remarkable enhancement in the electrolytes has also been demonstrated.[135,136] The capping of
mobility from ≈100 to 220 cm2 (V-s)−1 when the temperature the polymer electrolyte (PE), consisting of poly(ethylene oxide)
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FEATURE ARTICLE
(PEO) and lithium perchlorate (LiClO4), on top of MoS2 devices floating gate (few layer graphene). The information storage and
has driven a threefold enhancement in the mobility of MoS2 erasing process can be understood from its transfer character-
FETs owing to significant reduction in the resistance at the istics performed in two sweeping directions (Figure 9e) and
MoS2/metal interface and dielectric screening at the channel/ energy band diagram of the memory device in program and
dielectric interface.[135] Bao et al. showed that multilayer MoS2 erase states (Figure 9f). The large hysteresis (memory) window
FETs on polymethyl methacrylate (PMMA) exhibits an ambi- of 8 V allows the charging (program state) and discharging
polar behavior with a high mobility of 470 cm2 (V-s)−1 for elec- (erase state) of a floating gate that corresponds to the control
trons and 480 cm2 (V-s)−1 for holes.[136] gate sweeping direction from −15 to +15 V and from +15 to
There are some other methods, like phase engi- −15 V, respectively. The dynamic behavior of the switching
neering,[147,148] and insertion of graphene,[149] which have been between the program state and the erase state was achieved
explored for reducing contact resistance at metal–2D semicon- through the application of voltage pulses to the control gate at a
ductor interfaces. Kappera et al. reported a contact resistance of drain-source bias of 50 mV. A maximum program/erase (P/E)
200–300 Ω-µm, at zero gate bias, by locally inducing metallic current ratio of 104 of the nonvolatile memory device not only
1T phase of MoS2 on semiconducting 2H phase.[147] Such phase allows easy readout of the device state, but also enables mul-
engineering approach, where inducing a metallic phase of the tilevel storage. The successful operation of these initial proto-
same semiconducting material reduces the contact resistance, type memory cells will pave the way for efficient and scalable
has been found effective in reducing the contact resistance in devices through the engineering of blocking oxide layers using
other 2D systems as well.[148] Leong et al. demonstrated that 2D oxides. In addition to the demonstration of a wide range
insertion of an etched graphene as a buffer layer at metal-MoS2 of digital and logic circuits based on single layer MoS2 FETs,
interface can lead to low contact resistance.[149] They achieved analog circuits such as a small signal amplifier with a room
a contact resistance of 200 Ω-µm with nickel-etched-graphene temperature gain of four has also been reported using single
electrode on MoS2. layer MoS2 transistors.[151]
3.2. Integrated and Logic Circuits Based on MoS2 3.3. Optoelectronic Devices
The transistors based on single layer/few layer(s) MoS2 show The presence of a direct band gap in the visible frequency
promising mobility, high on/off current ratio, and record cur- range, coupled with its high carrier mobility makes monolayer
rent density. These appealing transistor device characteristics MoS2 an ideal candidate for various optoelectronic device appli-
enable 2D MoS2 to be a potential candidate for consideration cations like light generation (LEDs), light harvesting (solar cells)
toward building digital circuits comprising of Boolean logic and light sensing (photodetectors).[22,24,104,152] Several research
gates and memory components. In this direction, Radisavljevic scale prototype optoelectronic devices based on single or few
et al.[126] and Wang et al.[127] have demonstrated research scale layer MoS2 have already been demonstrated. A brief description
logic circuits based on exfoliated single layer and bilayer MoS2. of these devices is given below.
The first logic device, composed of two single-layer transistors
connected in series fabricated on a single flake of monolayer
MoS2, was demonstrated as the most basic logic gate: a logic 3.3.1. Photodetectors
inverter, capable of converting logic state 0 (low input voltage
state) into logic state 1 (high output voltage state) (Figure 9a–c). The sizable, thickness dependent band gap of MoS2 nanosheets
Connecting two transistors in parallel and using an external along with its large surface-to-volume ratio enable efficient
resistor as a load, a NOR gate was realized (Figure 9d). In a light detection over a wide range of wavelengths from ultra-
later report, Wang et al.[128] presented large scale integrated violet (UV) to the near infrared (NIR).[153,154] The irradiation
circuits based on CVD grown, single layer MoS2. The devices of photons of energy greater than the band gap of a semicon-
included fully integrated inverters and NAND gates operated in ductor gives rise to a photocurrent upon the separation of pho-
depletion mode. The demonstration of two types of universal togenerated electron–hole pairs (excitons) through an applied
logic gates, NAND and NOR, enables the realization of all other or built-in field. There are two fundamental designs for semi-
possible logic gates (AND, OR, XOR, etc.) using combinations conductor-based photodetectors: phototransistors (applied field
of NAND gates or NOR gates.[126,127] This is indeed an impor- or gate control) and photodiodes (built-in field).
tant step toward 2D nanoelectronics. The very first single layer MoS2 optoelectronic device, a phototran-
A static random access memory (SRAM) element has also sistor, was fabricated by Yin et al.[155] (Figure 10a,b). This device
been demonstrated using a pair of cross-coupled inverters.[127] exhibited an increased photocurrent for excitation wavelengths
This memory cell has two stable states, 0 and 1 at the output, below 670 nm with good photoresponsivity of 7.5 mA W−1
and can be set to logic state 1 (or 0) by applying low (or high) (Figure 10c,d), which is very high compared to graphene-based tran-
voltage to the input. Coupling the high conductivity of gra- sistors’ photoresponsivity (1 mA W−1).[156] Also, the transition speed
phene with the unique semiconducting properties of 2D MoS2, for current rise (OFF to ON) or current decay (ON to OFF) is quite
Bertolazzi et al.[150] demonstrated an all-2D nonvolatile memory fast (50 ms) which reveals a fast response/recovery speed of single
cell based on MoS2/graphene heterostructures with a floating layer MoS2 phototransistors. However, the response/recovery rate in
gate design. The device included not only a 2D channel (MoS2), these devices is still far lower than graphene transistors (tens of pico-
but also 2D source and drain contacts (graphene strips) and seconds),[157] which is accounted by the lower mobility of these back
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gated phototransistors (0.11 cm2 (V-s)−1). Lee et al.[153] demonstrated
FEATURE ARTICLE
transistor barely responded to red light due to its comparatively
transparent top gated phototransistors based on mono-, bi-, and equal gap (≈1.82 eV), but was still sensitive to green and UV lights.
trilayer MoS2 nanosheets. The bi- and trilayer transistors showed The thickness modulated linear mobility values were estimated to
good photoresponse to red, green, and UV light due to their respec- be as high as 80, 27, and 10 cm2 (V-s)−1 with longer response and
tive band gaps of ≈1.65 and ≈1.35 eV, whereas monolayer MoS2 recovery times of 1.5, 1, and 0.3 s respectively for single, double, and
Figure 9. a) Schematic of integrated circuit consisting of two top-gated transistors connected in series and b) cross-sectional view of the single layer
MoS2 transistor together with electrical connections. c) Output voltage as a function of input voltage for integrated MoS2 inverter and d) Output
voltage characteristics for different combinations of input voltage for NOR gate logic circuit based on single layer MoS2 transistor.[126] e) Transfer
characteristics of floating gate transistor in two sweeping directions with large hysteresis memory window of 8 V and f) simplified band diagram of the
memory device in program and erase states.[150] a–d) Reproduced with permission.[126] Copyright 2011, American Chemical Society. e,f) Reproduced
with permission.[150] Copyright 2013, American Chemical Society.
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FEATURE ARTICLE
Figure 10. a) Atomic force microscopy image of exfoliated monolayer MoS2. b) Optical microscopy image of first monolayer MoS2 phototransistor with
Ti/Au metal contacts for source and drain. c) The photocurrent (Ids) of transistor as a function of excitation wavelength for fixed optical power of 80 µW.
d) Variation in photoresponsivity with gate voltage at Vds = 1 V and constant optical power of 80 µW. The device shows maximum photoresponsivity of
7.5 mA W−1 for gate voltage of 50 V.[155] e) Photograph of CVD MoS2 monolayer grown on graphene/SiO2/Si. f) Schematic representation of graphene/
MoS2 phototransistor with source and drain contacts (Ti/Au = 5 nm/80 nm). g) Photoresponse and h) photogain characteristics of graphene/MoS2
phototransistor as a function of power densities.[104] a–d) Reproduced with permission.[155] Copyright 2012, American Chemical Society. e–h) Repro-
duced with permission.[104] Copyright 2014, Nature Publishing Group.
triple-layer transistors. In a later study, Choi et al.[154] demonstrated band gap of multilayer MoS2 is more advantageous than single
ultrasensitive bottom gate (Al2O3) multilayer MoS2 photodetectors layer MoS2 for wide range light detection and also that the bottom
with high photoresponsivity (>100 mA W−1) for a wide range of gate configuration is more viable for commercial fabrication than
wavelengths from UV to the NIR. They suggested that the narrow using a high-K material for a top gate.
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In a later study, Zhang et al.[158] studied the performance of and a recovery time of ≈110 µs and these devices are capable of
FEATURE ARTICLE
CVD grown monolayer MoS2 phototransistors in ambient con- broadband photodetection from visible to UV with a working
ditions. This study demonstrated that the photoresponsivity and temperature up to 200 °C. In their later study, the authors dem-
photogain of the devices are severely affected by the surface onstrated an improved responsivity (1.04 A W−1), photogain (up
accumulation of air adsorbates, which diffuses toward the MoS2/ to 24), and fast response/recovery times (40 50 µs−1) with the
SiO2 interface. The decrease of phototransistor performance use of trilayer MoS2 in Au MoS2 Au photodetectors.[164] The
was theorized to be due to the adsorbates from the air acting as reason for the faster response times/recovery times were attrib-
p-type dopants and leading to the dominance of p-type behavior, uted to the decrease of contact spacing from 8 to 4 µm, which
rather than n-type as is seen under vacuum. These p-type induces a higher electric field at the Au/MoS2 interface under
dopants on the surface or at the MoS2/SiO2 interface impose the same applied bias. In addition, PDs based on p-Si/n-MoS2
additional coulomb potential, which interacts strongly with the heterojunction have also been tested. However, these yielded
out of plane A1g mode, resulting in an abnormal increase in car- lower rise and fall times of 0.3 ms compared to conventional
rier scattering. Extensive Raman analysis of MoS2 monolayers MSM PDs. In a later study, Jariwala et al.[165] demonstrated a
has been done with laser exposure under an Ar ambience to gate-tunable p–n heterojunction photodetector through the
confirm the p-type doping of air and its effects on MoS2 Raman integration of p-type single-walled carbon nanotubes and n-type
modes. Surprisingly, Lopez-Sanchez et al.[159] demonstrated an MoS2 monolayer. Their photodetector exhibited an ultrafast
ultrasensitive monolayer MoS2 photodetector with a maximum photoresponse time (<15 µs) and a high spectral responsivity
photoresponsivity approaching 880 A W−1 at a wavelength of (≈0.1 A W−1) at 650 nm.
561 nm with a low intensity optical power of 150 pW. This value
is 106 times higher than that for the first graphene-based photo-
detectors,[157] and 105 times higher than that reported for the 3.3.2. Light Generation and Harvesting
first monolayer MoS2 phototransistors.[155] The enhancement
in photoresponsivity is mainly accounted for due to improved In 1939, R.S. Ohl from Bell Labs accidentally discovered
mobility as well as the contact quality and positioning tech- the p–n junctions during the purification process of Si
nique. Recently, Zhang et al.[104] built an all 2D-material photo- crystals.[166] This pioneering discovery led to the develop-
transistor with graphene/MoS2 (Figure 10e,f) based on the idea ment of a variety of optoelectronic devices for light gen-
of making use of the high carrier mobility in graphene to boost eration (LED), light harvesting (solar cells), and detection
the performance of phototransistor. The photodetector based of light (photodetectors). To date, efficient LEDs and solar
on the monolayer graphene/MoS2 heterostructure has shown cells employ technology that involves epitaxial III-V alloys
a remarkable photogain of 108 with a photoresponsivity of or multielemental materials (such as CIGS) due to the lack
107 A W−1 when exposed to 650 nm light at Vg = –10 V, Vds = 1 V, of simple materials having a direct band gap in the visible
and with an optical power density = 0.001 W m–2 (Figure 10g,h). spectrum. Recently, atomically thin TMDCs of molybdenum
The enhancement in light-to-current conversion efficiency of (Mo) and tungsten (W) have opened up fantastic avenues
the photodetector was attributed to the injection of light gener- for novel optoelectronic device designs due to the presence
ated carriers from MoS2 into graphene due to the presence of a of a finite and direct band gap in these materials.[6,25,26] The
perpendicular electric field at the 2D interface. In another study, first report on electroluminescence (EL) from single layer
Rathi et al.[160] highlighted the fundamental understanding of MoS2 was presented by Sundaram et al.,[22] in metal-MoS2
graphene-MoS2 phototransistor behavior, with their devices dis- Schottky junction through a hot carrier injection process.
playing a maximum photoresponsivity of ≈2.06 × 103 A W−1 at Although this study was considered a breakthrough for light
520 nm with an incident optical power density of 14 mW cm−2. emitting applications, the EL was locally confined and the
Although, the phototransistors have exhibited higher pho- high threshold power required for light emission and poor
toresponsivity, their relatively longer response time makes carrier-to-photon conversion efficiency (10−5) made these
simple photodiodes a more attractive option, where smaller devices almost impractical. The reason for locally confined
response times are expected. The easiest way to have a faster EL in lateral metal-MoS2 junctions was attributed to the full
response time is to separate the photogenerated carriers within depletion of the monolayer that prevents the efficient carrier
a diffusion length of the built-in field followed by a fast collec- injection across the entire monolayer. To achieve broad area
tion in a Schottky or p–n diode. The built-in field across the EL, vertical p–n structures were proposed that can enable
junction can be created through a metal-semiconductor junc- threshold-free recombination. In this way, Lopez-Sanchez
tion (Schottky junction), homojunction, or heterojunction. For et al.[167] introduced a novel, vertical 2D-3D heterostructure
ultrafast photo detection, back-to-back Schottky metal-semicon- diode composed of monolayer MoS2 (n-type) and p-Si for EL
ductor-metal (MSM) junctions have proven more successful devices and solar cells. The rectifying behavior of MoS2/p-
than simple Schottky junctions (M–S) for Si-and SiC-based pho- Si diode (Figure 11a) indicated that all related optoelectronic
todetectors (PDs).[161,162] The concept of M–S–M enables high- operations could be achieved using the combination of atom-
speed operation in MoS2-based PDs compared to traditional ically thin MoS2 and a 3D semiconductor. The application of
FET-based MoS2 phototransistors due to the reduced channel a forward bias induces light emission, resulting mainly from
length between the two M–S junctions.[26] Tsai et al.[163] demon- radiative recombination in MoS2, as radiative recombination
strated few layer MoS2 as MSM PDs with a high responsivity of in Si is less significant due to its indirect gap (Figure 11b).
0.57 A W−1 and a high photogain of 13.3. Moreover, the MoS2- Moreover, the EL is active over a large area (Figure 11c,d)
based MSM PDs exhibit a very fast response time of ≈70 µs compared to previous locally-gated electroluminescence[22] in
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FEATURE ARTICLE
Figure 11. a) Rectifying behavior of MoS2/p-Si diode. b) Band diagram of MoS2/Si heterojunction in equilibrium and forward biased conditions.
c) Intensity map of the EL device showing the entire area is active for light emission; device components superimposed over the EL spectrum. d) EL
spectrum acquired for a forward bias of V = 15 V and current of 1.8 µA.[167] e) Fabrication steps of monolayer MoS2/Si solar cell and f) J–V characteris-
tics of MoS2/Si solar cell.[102] a–d) Reproduced with permission.[167] Copyright 2014, American Chemical Society. e,f) Reproduced with permission.[102]
Copyright 2014, American Chemical Society.
metal-MoS2 Schottky junctions and exciton-related EL con- The results show that monolayer MoS2/Si solar cells hold
fined at the heterojunction edge of MoS2/p-Si.[168] The obser- promise for the integration of 2D materials with commer-
vation of large area emission is attributed to the hydrogen cially available Si-based electronics and optical devices.
passivation of the Si, resulting in the formation of a true Combining the advantage of high optical absorption of gra-
junction between MoS2 and p-Si. The heterojunction was phene and WS2, Bernardi et al.[24] studied the performance of
also operated as a solar cell and showed a maximum light- 1 nm thick solar cells based on MoS2/Graphene and MoS2/
to-electrical power conversion efficiency of 4.4%. There are WS2 bilayer. Their computational studies showed that such
also some other reports on ultrathin MoS2 PV devices; how- bilayer solar cells can reach over 1% power conversion effi-
ever, those reports are mainly based on multilayer MoS2 ciency in just 1 nm thickness, thus holding a packing power
nanosheets.[169,170] Recently, Tsai et al.[102] reported the density of 2.5 MW Kg−1, a value far superior to any known
photovoltaic operation over a large area using monolayer ultrathin solar cells.
MoS2 with p-Si to form a type-II heterojunction. Such a het- Although MoS2 has distinctive optical properties for strong
erojunction photovoltaic device achieved a power conver- light-matter interaction,[171] the lack of controlled doping
sion efficiency of 5.23%, which is the highest value reported strategies and the difficulty in achieving hole conduction in
among all monolayer TMDC-based solar cells (Figure 11e,f). monolayer MoS2 hinders the fabrication of atomically thin
www.afm-journal.de
homogeneous p–n junctions.[172] Earlier attempts to demon-
FEATURE ARTICLE
3.5. Multilayer van der Waals Heterostructures
strate the formation of stable MoS2 p–n junction devices by
using electric double layer gating,[146] or creating p-doped MoS2 The multilayer van der Waals structures are created by
by efficient plasma treatment,[173,174] was not feasible as these stacking various 2D atomic crystals on top of each other with
liquid gating and plasma treatments can damage the atomi- a chosen sequence.[6,190] The resulting stack represents an
cally thin structure. The exploitation of intrinsically p-type artificial van der Waals material analogous to Lego blocks—
TMDCs having different band gaps and work functions,[175] where each block is an individual 2D material[6] (Figure 12a).
led to van der Waal p–n heterostructures of p-WSe2/n-MoS2, The concept of designing artificial heterostructures has been
which are promising for applications in optoelectronic devices demonstrated experimentally by stacking graphene/hBN or
such as light emitting diodes,[152] solar cells,[176,177] and graphene/MoS2/graphene (GMG) or graphene/MoS2/metal
photodiodes.[178] (GMM) to realize vertical field effect transistors (VFETs), and
superlattices (Figure 12b).[191–196] The use of hBN in conjunc-
tion with graphene produces high electronic quality hetero-
3.4. Valleytronic Applications structures,[197,198] but causes an insufficient on/off current
ratio due to hBN’s larger band gap (≈5.97 eV). Larger on/off
Single layer MoS2 has attracted tremendous attention recently ratios would be expected for a graphene/MoS2 VFET, owing
because of its potential application in valleytronics.[179–181] to MoS2’s smaller band gap as compared to hBN. The earliest
Valleytronics is a new paradigm of electronics that utilizes experiments on MoS2-based heterostructures were conducted
materials in which the conduction (valence) band exhibits by Britnell et al.[192] utilizing a vertical stack consisting of gra-
two or more minima (maxima) at equal energies but at dif- phene/MoS2/graphene (GMG) for tunneling field effect tran-
ferent momentum values.[182–184] Thus, in addition to charge sistors. In that report, the authors demonstrated two different
and spin, these materials have an additional degree of types of graphene-based heterostructures with few layer hBN or
freedom to play with.[185] Valley polarization in these mate- MoS2 acting as the insulating tunnel barrier. Tunneling transis-
rials is achieved by controlling the number of charge carriers tors utilizing MoS2 exhibited three orders of magnitude higher
in the valleys. Devices based on selective valley conduction on-off ratio (≈104) compared to those utilizing hBN-based (≈50).
are termed as valleytronic devices. Monolayer MoS2 is consid- Yu et al.[199] designed an n-channel VFET by sandwiching few-
ered a promising material for valleytronic device applications layer MoS2 between monolayer graphene and an ohmic-contact
since its conduction band and valence band edges have two metal top electrode (GMM). The optimized VFET delivered
energy degenerate valleys at the corners of the first Brillouin a high on-current density of up to 5000 A cm–2, which is 3–5
zone.[179–181] Moreover, unlike graphene, the breaking of orders of magnitude greater than the recently reported ver-
inversion symmetry, strong spin–orbit coupling and exist- tical tunneling transistor,[195] and graphene barristor,[200] while
ence of a direct band gap are added advantages in the case of retaining a high on-off ratio of >103 (Figure 12c,d). Under nega-
monolayer MoS2. tive Vsd regime the Schottky barrier at the contact between gra-
The most challenging task in valleytronics research is to phene and MoS2 plays a dominant role in current modulation,
identify a suitable technique to address the carriers in dif- whereas under positive Vsd conditions the top metal–MoS2 con-
ferent valleys separately. Schemes based on inversion sym- tact plays the primary role in determining the current modula-
metry breaking, which can lead to circular dichroism in tion (Figure 12e). An extensive study was conducted to further
different k-space regions, have been suggested by many understand the charge transport mechanism in their VFETs by
researchers.[185,186] Since monolayer MoS2 does not have an considering three different device configurations that included
inversion symmetry, selective photoexcitation by circularly a graphene–MoS2–graphene tunneling barrier (GMG TB), a
polarized light can be used as a means of controlling the graphene–MoS2–graphene Schottky barrier (GMG SB) and a
valley population.[187,188] Carriers in different valleys can be graphene–MoS2–metal (Ti) Schottky barrier (GMM SB) with
addressed by controlling the angular momentum of the exci- variable MoS2 thicknesses. It was found that the charge trans-
tation photon (i.e., helicity of the light). Photons with a given port mechanism in the GMG heterostructres and their variants
circular polarization excite the electrons of only a particular depends on the thickness of the MoS2 layer, consistent with the
spin. Because of the strong spin–orbit interaction in MoS2, the earlier reports.[192] For ultrathin MoS2 layers (<4 nm), the tun-
momentum of the electrons, which are excited by the photons, neling current is the dominant component in charge transport,
is determined by their spin. Therefore, right and left circularly whereas for thicker MoS2 films (4–40 nm), thermionic emis-
polarized light can selectively populate two different valleys in sion current is the dominant component.
monolayer MoS2. Moreover, it has been shown that in bilayer In a later report, Myoung et al.[201] showed that the cur-
MoS2, the inversion symmetry can be broken by an external rent on-off ratio of the vertical graphene field-effect transistor
electric field applied normal to the plane. This leads to a poten- can be enhanced by up to 106 by replacing the top graphene
tial difference between the individual layers and allows the con- electrode (GrT) by an armchair or zigzag graphene nanor-
trol of valley polarization.[189] ibbon (AGNR or ZGNR), which is one order larger than their
Despite the promising nature of single and bilayer MoS2 conventional GMG heterostructures. The improvement in
for valleytronic applications, the technology is still in infancy. the current on-off ratio of graphene/MoS2/AGNR was attrib-
Much more research is needed to develop techniques for selec- uted to the one-dimensional nature (van Hove singularity) of
tively populating the valleys and also for selectively detecting AGNRs. Myoung et al.[201] also exploited the magnetic proper-
the corresponding valley polarized current. ties of atomically thin MoS2 by calculating the spin-dependent
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FEATURE ARTICLE
Figure 12. a) Artificial van der Waal heterostructures (left panel) and analogous Lego blocks (right panel).[6] b) Schematic representation of graphene-
hBN superlattices consisting of stacked multilayers with corresponding HAAD STEM image.[194] c) Isd–Vsd output characteristics of GMM vertical field
effect transistor shown in inset and d) Corresponding transfer characteristics. e) Schematic representation of band structure at negative Vsd and posi-
tive Vsd for positive and negative gate voltages.[199] f) Schematic representation of graphene/m-MoS2/graphene heterostructure for spin-polarization.
g,h) Spin-dependent current density and spin-polarization through graphene/m-MoS2/graphene for hole and electron.[201] a) Reproduced with permis-
sion.[6] Copyright 2013, Nature Publishing Group. b) Reproduced with permission.[194] Copyright 2012, Nature Publishing Group. c–e) Reproduced
with permission.[199] Copyright 2013, Nature Publishing Group. f–h) Reproduced with permission.[201] Copyright 2013, American Chemical Society.
tunneling current through a magnetic MoS2 (m-MoS2) in GMG recently, Huo et al.[178] demonstrated vertical heterojunctions
heterostructures (Figure 12f). Their calculations predicted that comprising of p-WSe2/n-MoS2, which are shown to exhibit dis-
the graphene/m-MoS2/graphene heterostructure can act as a tinct rectification behavior as well as ambipolar conduction with
spin-filter for holes due to the difference in spin-splitting near an n-type on/off ratio of 102 and a p-type on/off ratio exceeding
the K-valley of m-MoS2. The spin splitting is about 50 times 104 from the p-channels of WSe2 and n-channels of MoS2.
larger in the valence band (δv ≈ 145 meV) than in the conduc- In addition to the earlier demonstrations of grapahene/
tion band (δc ≈ 3 meV). The large spin-splitting energy in the MoS2-based vertical heterostructures for novel electronic appli-
valance band leads to a strong spin-polarization in the hole cations, these heterostructures have also been exploited for
tunneling current, Pj ≈ 0.9–0.97 (Figure 12g,h). Most recently, optoelectronic device applications by making use of the direct
Tian et al.[202] demonstrated vertical field effect Schottky barrier band gap of MoS2. Yu et al.[204] used vertically stacked GMG and
transistors based on graphene/MoS2 heterostructures with a GMM heterostructures to obtain highly efficient, gate-tunable
large modulation in the device current (on-off ratio of 105) and photocurrent generation and photodetection. They demon-
mobility (58.7 cm2 (V-s)−1). Large scale, fully integrated logic cir- strated that the amplitude and polarity of the photocurrent in
cuits (inverters and NAND gates) and related chip technology the gated vertical heterostructures can be readily modulated
have also been reported using graphene/MoS2 heterostructures, by the electric field of an external gate to achieve a maximum
where MoS2 serves as the transistor channel and graphene external quantum efficiency of 55% with corresponding photo-
as the contact electrodes and circuit interconnects.[203] Most responsivity of ≈0.22 A W−1 and faster response times (<50 µs).
www.afm-journal.de
Acknowledgements
FEATURE ARTICLE
Most recently, MoS2-graphene-metal hybrid structures were
demonstrated to work as multifunctional photoresponsive
The authors thank US NSF for support through Grant Nos. 1407650 and
memory devices with a room temperature photoresponsivity of 1121252 (MRSEC). Y.P.V.S. and K.J.S. thank UGC, Government of India,
up to 5 × 108 A W−1,[205] which is the highest to date among the for providing support under Raman postdoctoral fellowship scheme.
graphene-based photodetectors. Similar to graphene/MoS2 PDs,
a novel semiconducting PD consisting of MoS2-WS2 has been Received: October 1, 2015
shown to exhibit a high photoresponsivity of 1.42 A W−1.[190] A Revised: November 20, 2015
novel heterostructure based on MoS2 PDs comprising of p-type Published online: February 22, 2016
black phosphorus/n-type monolayer MoS2 has also been dem-
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