Review

Cite This: Chem. Rev. 2018, 118, 6091−6133 pubs.acs.org/CR

Chemical Vapor Deposition Growth and Applications of Two-

Dimensional Materials and Their Heterostructures
Zhengyang Cai,† Bilu Liu,*,† Xiaolong Zou,† and Hui-Ming Cheng*,†,‡,§
†
Shenzhen Geim Graphene Center (SGC), Tsinghua−Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen,
Guangdong 518055, People’s Republic of China
‡
Shenyang National Laboratory for Materials Sciences, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, Liaoning
110016, People’s Republic of China
§
Center of Excellence in Environmental Studies (CEES), King Abdulaziz University, Jeddah 21589, Saudi Arabia
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ABSTRACT: Two-dimensional (2D) materials have attracted increasing research

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interest because of the abundant choice of materials with diverse and tunable electronic,
optical, and chemical properties. Moreover, 2D material based heterostructures
combining several individual 2D materials provide unique platforms to create an
almost infinite number of materials and show exotic physical phenomena as well as new
properties and applications. To achieve these high expectations, methods for the scalable
preparation of 2D materials and 2D heterostructures of high quality and low cost must
be developed. Chemical vapor deposition (CVD) is a powerful method which may meet
the above requirements, and has been extensively used to grow 2D materials and their
heterostructures in recent years, despite several challenges remaining. In this review of
the challenges in the CVD growth of 2D materials, we highlight recent advances in the
controlled growth of single crystal 2D materials, with an emphasis on semiconducting transition metal dichalcogenides. We
provide insight into the growth mechanisms of single crystal 2D domains and the key technologies used to realize wafer-scale
growth of continuous and homogeneous 2D films which are important for practical applications. Meanwhile, strategies to design
and grow various kinds of 2D material based heterostructures are thoroughly discussed. The applications of CVD-grown 2D
materials and their heterostructures in electronics, optoelectronics, sensors, flexible devices, and electrocatalysis are also
discussed. Finally, we suggest solutions to these challenges and ideas concerning future developments in this emerging field.

CONTENTS 4.2. Growth of Continuous 2D Films on Rigid

Substrates 6103
1. Introduction 6092 4.2.1. MOCVD Method 6103
2. Overview of the Key Parameters in the CVD 4.2.2. Conventional CVD Method 6105
Growth of 2D Materials 6093 4.2.3. Thin Film Deposition Method 6105
2.1. Precursor 6094 4.3. Growth of Continuous 2D Films on Flexible
2.2. Temperature 6094 Substrates 6106
2.3. Substrate 6094 4.3.1. Direct Growth on Flexible Substrates 6106
2.4. Pressure 6095 4.3.2. Postgrowth Transfer 2D Materials onto
2.5. Other Parameters 6095 Flexible Substrates 6107
3. CVD Growth of Single Crystal 2D Materials 6095 5. CVD Growth of 2D Material Based Heterostruc-
3.1. Theory of 2D Materials Growth by CVD 6095 tures 6107
3.2. Controlled Growth of Single Crystal 2D 5.1. Vertical 2D Heterostructures 6108
Materials 6096 5.1.1. Metal/Semiconductor 6108
3.2.1. Grain Size 6096 5.1.2. Semiconductor/Semiconductor 6109
3.2.2. Layer 6097 5.1.3. Semiconductor/Insulator 6111
3.2.3. Orientation 6098 5.1.4. Metal/Insulator 6111
3.2.4. Morphology 6100 5.2. Lateral 2D Heterostructures 6112
3.2.5. Phase 6101 5.2.1. Metal/Insulator 6112
3.2.6. Doping 6101 5.2.2. Semiconductor/Semiconductor 6112
3.2.7. Quality and Defects 6102
4. CVD Growth of Wafer-Scale Continuous 2D
Material Films 6103
4.1. Motivation for and Challenges of Growing Special Issue: 2D Materials Chemistry
Wafer-Scale Continuous and Homogeneous Received: September 5, 2017
2D Material Films 6103 Published: January 31, 2018

© 2018 American Chemical Society 6091 DOI: 10.1021/acs.chemrev.7b00536

Chem. Rev. 2018, 118, 6091−6133
Chemical Reviews Review

5.2.3. Metal/Semiconductor 6113 example, 1D and 0D materials are usually prepared by bottom-up
5.3. Other Dimension/2D (xD/2D) Heterostruc- synthesis approaches, while 2D materials can be prepared by
tures 6113 either bottom-up synthesis or the top-down exfoliation of bulk
5.3.1. 1D/2D 6113 layered materials. In addition, layer−layer interactions in 2D
5.3.2. 0D/2D 6114 materials can result in unusual material properties and provide
6. Applications of CVD-Grown 2D Materials and excellent platforms to study fundamental physics. As a
Their Heterostructures 6115 representative 2D material, graphene, a monolayer of graphite,
6.1. Electronics 6115 exhibits extraordinarily high charge carrier mobility, along with
6.2. Optoelectronics 6116 many other excellent properties including high thermal
6.2.1. LEDs 6116 conductivity, high mechanical strength, large surface area and
6.2.2. Photodetectors 6117 broadband optical absorption, etc.1,2 Intriguing physical
6.2.3. Solar Cells 6118 phenomena such as the quantum hall effect and a Berry phase
6.3. Sensors 6118 have been reported in graphene.3 These features make graphene
6.4. Flexible and Wearable Devices 6119 a “superstar” in condensed matter physics and materials sciences
6.5. Hydrogen Evolution Reactions 6119 and have promoted extensive research on 2D materials
7. Concluding Remarks and Outlook 6121 analogous to graphene, including hexagonal boron nitride (h-
7.1. Improvement and Innovation of CVD Growth BN), transition metal dichalcogenides (TMDCs), black
Systems 6121 phosphene, silicene, germanene, etc., forming a large family of
7.2. Salt-Assisted Growth of TMDCs: A General 2D materials.4,5 Importantly, the 2D materials family exhibits a
and Efficient Route 6122 wide spectrum of electronic properties covering metals,
7.3. High Quality 2D Materials 6122 semimetals, semiconductors with various energy band gaps,
7.4. Large Single Crystal and Fast Growth and also insulators.6,7 Besides their wide range of electronic
Methods: A Long Way to Go 6122 properties, 2D materials also have high surface areas, dangling
7.5. Exploration of Novel 2D Materials with Exotic bonds, and surface state free nature, and may exhibit strong
Properties 6122 spin−orbit coupling and quantum spin Hall effects, making them
7.6. Low Temperature Growth of 2D Materials for attractive for studying new physics and exploring devices using
Flexible Device Applications 6123 new concepts.8,9 Moreover, when different 2D materials stack or
7.7. Heterostructures: Variations and Easy Growth 6123 merge, vertical or lateral heterostructures with an atomically
7.8. High-Performance Scalable Electronics and sharp interface can be obtained, providing perfect platforms to
Optoelectronics 6123 investigate layer−layer interactions at the atomic scale as well as
Author Information 6123 devices with new functions.10−12 Taken together, these unique
Corresponding Authors 6123 features of 2D materials allow them to have potential in many
ORCID 6123 fields including electronics, optoelectronics, sensors, flexible and
Notes 6123 wearable devices, catalysis, and many others.
Biographies 6123 The properties of 2D materials are closely related to their
Acknowledgments 6124 structures, including size, number of layers, morphologies,
References 6124 orientations, phases, doping, defects, grain boundaries, etc.13
For instance, (i) the number of layers, the phases, and any doping
of 2D materials each have a crucial influence on the electronic
1. INTRODUCTION structures, and further determine the performance of 2D material
Advanced materials play important roles in our daily lives. It is based electronic and optoelectronic devices.14,15 (ii) High quality
well-known that human civilization can be classified by the key 2D materials are often defect-free or contain few grain
material used at the time, e.g., Stone Age and Bronze Age. boundaries, resulting in a high charge mobility and a low
Historically, people have spent thousands of years to improve the interface scattering and excellent electronic performance. (iii)
properties of materials by playing with their chemical Large area continuous 2D crystals with uniform properties are of
compositions, structures, processing recipes, etc. Since the great importance for devices with reproducible performance. For
1980s, dimensionality has entered the horizons of condensed practical applications of 2D materials, especially in electronics
matter physics and materials science research and triggered rapid and optoelectronics, high quality and large area materials with
developments in low-dimensional (LD) materials. In compar- controlled properties are prerequisites. This fact calls for a deep
ison to traditional bulk materials which are commonly called understanding of the material growth mechanism for preparing
three-dimensional (3D) materials, LD materials refer to 2D materials with controlled quality, structure, and other
materials that have a nanoscale size in at least one dimension. properties.
LD materials exhibit unique properties originating from the Generally, mechanical exfoliation, liquid exfoliation, and vapor
quantum confinement effect of their nanoscale size, which phase growth are commonly adopted strategies for 2D material
provides researchers the ability to precisely tune the material’s preparation. For example, the Scotch-tape-based mechanical
properties at the atomic level. In general, LD materials can be exfoliation method led to the discovery of graphene,16 and it is
divided into three categories: two-dimensional (2D), one- still an important method for preparing virtually any 2D material.
dimensional (1D), and zero-dimensional (0D). It can produce the highest quality 2D materials, making it an ideal
Of the above three types of LD materials, 2D materials are tool for fundamental physics studies.17 However, it is obvious
rather unique because they have bulk counterparts, i.e., layered that such a method is not suitable for the large-scale production
materials. In contrast, neither 0D nor 1D materials have such of 2D materials. In addition, it is difficult to control the number of
bulk counterparts. This feature leads to several noticeable layers and their size, orientation, and phase using this technique
differences between 2D materials and 1D or 0D materials. For since this method highly relies on the experience of researchers.
6092 DOI: 10.1021/acs.chemrev.7b00536
Chem. Rev. 2018, 118, 6091−6133
Chemical Reviews
Figure 1. Overview of the CVD growth of 2D materials, from single crystals to continuous films, and further to 2D material based heterostructures, as
well as their device applications. Reprinted from ref 24. Copyright 2015 American Chemical Society. Reprinted with permission from ref 25. Copyright
2015, Rights Managed by Nature Publishing Group. Reprinted with permission from ref 26. Copyright 2015, Rights Managed by Nature Publishing
Group. Reprinted from ref 27. Copyright 2014 American Chemical Society.
On the other hand, a liquid phase exfoliation method is suitable
for the low-cost production of 2D materials with scale-up
capability. However, the size and quality of solution-prepared 2D
materials are of concern for some applications.18 In this regard,
the vapor phase based direct growth approaches, especially
chemical vapor deposition (CVD), provide a scalable and
controllable way to grow high quality and large area 2D materials
with a reasonable cost. These advantages make CVD very
important for fundamental research and exploring the
applications of 2D materials.19,20
Several correlations have been discovered between the
parameters used in CVD and 2D materials produced. On one
hand, CVD is a process in which gaseous materials react in the
vapor phase or on the surface of substrates, and thus form solid
products that are deposited on the substrates. The number of
layers, their size, morphology and orientation, and the
introduction of any dopants or defects can be controlled by
playing with the growth parameters such as temperature,
chamber pressure, carrier gas flow rate, relative amounts of
source materials, and source−substrate distance. Recently,
modifications of 2D material growth methods have been widely
used to fabricate their heterostructures, making the 2D family
more versatile than uniphase 2D materials. On the other hand,
theoretical and technological advances in the growth of 2D
materials can improve the development of the CVD method
itself. Compared with traditional CVD approaches to grow silica,
tungsten, and diamond, some modified CVD methods have been
developed to grow large area and high quality 2D materials.21 For
example, Wu et al. developed a local feed method by supplying
the source gas to a single point with a small area in the CVD
furnace to create only one nucleus, which later grew into an inch
size single crystal graphene domain.22 In this regard, the
development of CVD methods and 2D material growth may
together promote the rapid development of research into 2D
materials and accelerate their wide use with the availability of
large-scale and high quality CVD-grown samples.
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In the past few years, researchers have made great achieve-
ments in the CVD growth of 2D materials and the exploration of
their use.23 Here, we present a comprehensive review of recent
progress in the controllable growth of 2D materials and their
heterostructures, as well as the applications of these advanced
materials in various areas (Figure 1). We focus on both the
fundamental nucleation and growth mechanism of 2D materials,
as well as technologies developed on how to grow large single
crystal 2D material domains, wafer-scale 2D material films, and
the recently emerging 2D material based heterostructures. We
also list several key challenges and opportunities in this field
related to both the growth and applications of 2D materials, and
suggest how these problems might be solved to further push
developments in this important field.
2. OVERVIEW OF THE KEY PARAMETERS IN THE CVD
GROWTH OF 2D MATERIALS
In general, 2D materials can be prepared by two strategies, i.e.,
top-down-based exfoliation methods and bottom-up-based
growth methods. The former includes mechanical and liquid
phase exfoliation, while the latter includes CVD, physical vapor
deposition (PVD), vapor phase transport (VPT), molecular
assembly, atomic layer deposition, etc. Note that, in this review,
we use the term “CVD” as a general term to cover several vapor
transport based methods including CVD, PVD, VPT, and other
closely related techniques. Such CVD-based vapor phase growth
methods are powerful in preparing high quality 2D materials,
because they can grow materials with a high quality and scale-up
capability. Hence, it is important to highlight several key CVD
parameters in growing 2D materials.
The properties of 2D materials are largely dependent on their
size, morphology, phase, any interfaces present, etc. These
features can be controlled by rational design and careful tuning of
the CVD growth processes. Therefore, it is important to
understand the general mechanisms of CVD growth, i.e., how
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Chemical Reviews
parameters such as the precursor, substrate, pressure, and
temperature affect mass and heat transport, interface reactions,
and consequently the growth of the materials (Figure 2).
Figure 2. Schematic showing how various parameters including
precursor, temperature, pressure, and substrate affect the thermody-
namics and kinetics in the CVD growth of 2D materials.
2.1. Precursor
Precursors serve as reactants in the CVD process. Briefly, three
reactions, including thermal decomposition reactions, chemical
synthesis reactions, and chemical transport reactions, are
generally involved in the conversion of precursors into the
desired products. In a commercial CVD setup to grow silicon,
vapor sources along with a carrier gas (SiH4 or SiH2Cl2, H2, and
Ar) are directly introduced into the reaction system, and the use
of these gaseous precursors allow precise control of the number
of molecules involved (e.g., 1 sccm at atmospheric pressure
equals 7.4 × 10−7 mol/s; here sccm stands for standard cubic
centimeters per minute) by changing the flow rate and partial
pressure of each precursor. In addition, a large amount of
hydrogen gas in the reactor can terminate any broken or dangling
bonds and result in high quality samples. However, high purity
precursors are often needed to avoid detrimental contaminants
and unwanted side reactions.
Basically, this is also true for graphene deposition, where
gaseous sources such as CH4 and H2 are commonly used as
precursors. This type of gaseous precursor is convenient for the
CVD process due to the easy and accurate control of the gas flow
rate over a wide range, allowing one to precisely control the
structure, morphology, and size of the graphene. In addition, by
introducing gaseous NH3 or PH3, the graphene can be doped
with N or P atoms.28,29 In comparison, solid sources are currently
most commonly used for the growth of TMDCs. In these
processes, transition metal oxides (e.g., MoO3, WO3) or
chlorides (MoCl5) or metal foils often serve as metal
(molybdenum or tungsten) sources while S or Se powders act
as the source of sulfur or selenium. These solid precursors require
very accurate temperature control of the source zone since the
vapor pressure of solid materials is very sensitive to temper-
ature.30 Therefore, the controllability of TMDC growth is a real
challenge and the technology for it is much less mature than that
for graphene growth. The use of all gaseous precursors such as
Mo(CO)6, CS(CH3)2, and H2S has been shown to be able to
improve the uniformity of as-grown TMDC films.25
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2.2. Temperature
Generally speaking, the temperature in a CVD system may affect
the flow of the carrier gas, the chemical reactions of precursors in
the gas phase, and the deposition rate of products on the
substrate. These features suggest that temperature can determine
the composition and uniformity of the products. High quality
products can usually be obtained at relatively high temperatures
but only at the price of high energy consumption and limited
suitable substrates. In a more important aspect, temperature may
result in fast diffusion of species in the gas flow on the order of
105 cm/s, which is much higher than the flux velocity in a typical
CVD process. This would result in a concentration gradient,
especially with respect to mass transport near the solid surface in
the CVD system.
Temperature plays an even more important role in TMDC
growth than in graphene growth in the following two aspects.
First, as mentioned above, the temperature in the source zone is
important because a slight temperature change may lead to a
large change in the saturation pressure of gasified solid
precursors, which in turn will significantly affect the growth of
TMDCs. Second, the temperature in the reaction zone can affect
the mass transport of species and their reaction at the vapor−
solid interface, providing an effective approach to adjusting the
reaction rate. The temperature in the source zone is used to gasify
solid precursors such as sulfur and selenium in TMDC growth. In
this case, the higher the temperature, the higher the gas
concentration, and this kind of sufficient supply of precursors can
make the growth controlled by the chemical reaction rate. On the
other hand, a relatively low temperature would result in a mass
transport limited growth mechanism. Furthermore, with the
consumption of solid precursors, their concentrations in the gas
phase would decrease gradually, leading to a gradient of
precursor feed in TMDC growth thus making CVD growth
difficult to control. For nucleation at the vapor−solid interface,
generally speaking, a high temperature leads to a thermodynamic
process while a low temperature leads to a kinetic process. In
recent experiments, multilayer MoSe2 nucleation, that is when
the upper triangles grow from the same nucleation site at the
center of the bottom triangle, was found to occur at temperatures
higher than 800 °C, suggesting that temperature acts as an
important factor in controlling the number of layers of 2D
materials.31 It is therefore obvious that, for growth at this
interface, a high temperature would accelerate the growth rate.
The importance of growth temperature on the layer size, number
of layers, and shape of as-grown WSe2 flakes has been
systematically studied,24 showing the importance of temperature
on the controlled growth of TMDCs.
2.3. Substrate
“Substrate” refers to where the material is deposited in the CVD
process, but more than that, the substrate provides other
functions. Catalytic active nickel and copper substrates are
usually used as substrates as well as catalysts for multilayer and
monolayer graphene growth, due to their different carbon
solubilities and catalytic abilities. In contrast, inert Si/SiO2,24
mica,32 and polyimide33 are commonly used substrates for 2D
TMDC growth, while the use of metals such as gold or tungsten
foils for TMDC growth has also been reported.34−36 Specifically,
the microstructure and lattice structure of the substrate can
significantly affect the growth of 2D materials. For the simple
fabrication of electronic and optoelectronic devices, TMDC
materials are commonly grown on Si/SiO2 substrates without
adding any catalysts. On this kind of SiO2/Si substrate, certain
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Chemical Reviews
substances such as perylene-3,4,9,10-tetracarboxylic acid tetra-
potassium salt (PTAS), perylene-3,4,9,10-tetracarboxylic dia-
nhydride (PTCDA), and reduced graphene oxide (rGO) were
used to promote the nucleation and growth of TMDCs.37 In
addition to these seeding promoters, additives such as alkali
metal halides (NaCl, KI, KCl, and NaBr), sodium cholate, and
NaOH have been increasingly frequently used to promote the
growth of TMDCs. Such additives, or growth promoters, can
react with high melting point precursor (such as WO3 and
MoO3), and form volatile intermediates.38−43 Via adding such
growth promoters, the domain sizes of TMDCs usually increase,
and the growth windows become broader. However, the
functions of such growth promoters are not very clear, and
more efforts are needed to gain better understanding about the
mechanism of these growth promoters. However, a very different
situation occurred for sapphire substrates. Due to the specific
lattice orientation of c-plane sapphire and the atomically smooth
sapphire terraces on the surface, TMDC growth on this kind of
substrate showed a specific orientation preference, related to the
crystal symmetry and the surface terraces of the substrates.44,45
For metal foil substrates, the crystallography of gold can be used
to determine the nucleation and domain size of TMDCs by
selecting different facets. This preferential nucleation and growth
on specific facets originates from the facet-dependent binding
energy between TMDCs and substrates.46 In addition, the
orientation of the substrate is important for morphology control
of the as-grown sample. For example, a MoS2 continuous film
with a domain size as large as 20 μm was grown by using a growth
substrate oriented in a vertical position in the chamber rather
than a horizontally oriented growth substrate; in this case, the
uniformity of the precursor feedstock was significantly
improved.47
2.4. Pressure
Pressure in a CVD chamber can vary over a wide range from a few
atmospheres to several millitorr or even lower, and this has a
tremendous influence on the gas flow behavior. At a low pressure,
the volume flow and the velocity of gas are much increased for
the same molar flow, while the precursor concentration decreases
based on the ideal gas equation PV = nRT. As a result, the low
concentration and high velocity of the mass feed of the precursor
can make the reaction more controllable.
Hence, for the growth of a wafer-scale, continuous TMDC
film, a low pressure CVD approach is usually used.48,49 In
addition, the partial pressure of a specific precursor can affect the
layer-by-layer mechanism for TMDC growth. In the growth of
MoS2, the partial pressure of Mo(CO)6 plays a vital role. At a low
pressure, the nucleation of the second layer can happen only at
the grain boundaries, whereas at a high pressure nucleation
occurs randomly on the top of the first layer and leads to a
mixture of monolayer and multilayer products.
2.5. Other Parameters
In addition to thermal CVD where heat is a major means of
breaking chemical bonds in the precursors so as to promote
following reactions, there are many other methods of achieving
this purpose, for example, a plasma, light, or a laser. Among these
modified CVD methods, plasma-enhanced CVD (PECVD) is a
powerful tool to enable many film deposition processes that are
impossible or very difficult to achieve by solely adjusting
temperatures and other parameters in a typical thermal CVD
reaction.50 A plasma is any gas where atoms or molecules are
ionized into negatively charged electrons, positively charged ions,
and neutral species. The electrons are so light and have a high
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temperature of thousands of kelvin. Such high temperatures can
induce unusual processes that would not happen at regular
temperatures, such as the dissociation of precursor molecules.
Moreover, interactions between the surface and energetic ions
lead to an increase in the density of the deposited film, and help
remove contaminants and improve the quality of the films. It
should be noted that the inductively coupled plasma CVD (ICP-
CVD) method permits film deposition at an even lower
temperature than normal PECVD. These methods have great
potential in achieving high quality 2D films at moderate
temperatures, which is important for growth on polymeric or
glass substrates.
Different from the conventional growth of graphene on metal
foils (e.g., Cu, Ni) at temperatures around 1000 °C,51,52 Sun et al.
reported the growth of graphene on glass without any catalyst at
low temperatures in the range 400−600 °C by the PECVD
method.53 The structure and electrical properties of the as-grown
graphene have been shown to be well-tailored during PECVD. In
addition, this method also works for TMDCs. For example, Kim
et al. used the PECVD approach and realized the growth of MoS2
films at temperatures from 150 to 200 °C using a Mo thin film
and H2S gas as precursors.54 Notably, ICP-CVD provides a
powerful approach to grow TMDC materials with novel
structures. For example, Lu et al. used ICP-CVD to strip the
top-layer S atoms from an as-grown MoS2 monolayer and
obtained intermediate MoSH, and followed this with thermal
selenization to grow Janus MoSSe monolayer TMDC materi-
als.55 These results demonstrate that advanced CVD systems can
help to create new materials and make 2D materials grown in an
easier way.
3. CVD GROWTH OF SINGLE CRYSTAL 2D MATERIALS
Recent studies have shown that CVD is very powerful in
synthesizing 2D materials. For practical applications of CVD-
grown 2D materials, it is crucial to improve the reproducibility of
the growth process, which needs a deep understanding of the
general growth mechanism. Hence, the link between the theory
of 2D material growth and the CVD process needs to be studied
and understood. Single crystal materials provide a valuable
platform to investigate fundamental nucleation and growth
mechanisms, as well as develop approaches to controlling the
properties of the materials. In this section, based on an
understanding of the growth mechanisms of 2D materials,
theory and practical approaches on how to control several key
features of the single crystals, including their size, number of
layers, orientation, morphology, and phase, and any dopants and
defects they contain are discussed.
3.1. Theory of 2D Materials Growth by CVD
In early research, it was reported that a typical growth process of
2D TMDCs consists of evaporation and reduction of metal oxide
solid precursors to suboxides, which further react with reducer
vapors (such as sulfur or selenium) to form TMDCs on a
substrate. Notably, a metastable nanoparticle reaction inter-
mediate (MOxXy) was suggested to serve as both metal source
and nucleation site for the subsequent formation of layered
TMDCs.56,57 In the CVD growth of 2D materials, various
parameters including temperature, gas flow rate, pressure, type of
substrate, etc. have effects on the nucleation and growth of 2D
materials. So far, several nucleation and growth models for 2D
materials have been reported, including layer-by-layer (LBL),
layer-over-layer (LOL), screw-dislocation-driven (SDD),58 and
dendritic growth models.59 Here, degrees of supersaturation of
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the reactants play a role in determining the growth modes of the
materials.
LBL growth is usually observed in 2D graphene and TMDC
growth processes. Because nucleation of new layers has to
overcome high energy barriers, high supersaturation conditions
are usually necessary to initiate the nucleation and enable a
reasonable crystal growth rate for LBL growth.60 For the growth
of 2D materials in a CVD system, good control of the precursor
concentration may lead to precise control of the number of layers
and well-stacked vertical heterostructures. The SDD growth
model was previously reported in the solvent synthesis of one-
dimensional oxides, hydroxides, and nitrides.61 Recent research
indicates that 2D materials grown by CVD under low
supersaturation conditions also obey a SDD model.62,63 It is
shown that a new layer is initiated at the center of the first layer,
and grows faster than the bottom one. When the upper layer
catches up with the bottom layer, its growth will stop. This
growth model results in a pyramid-like morphology with steps
and helices inside, which exhibits a unique thickness-
independent vertical conductance as shown in a recent study.64
This growth model provides a potential way to control the
number of layers or even stacking rotation in 2D materials.
3.2. Controlled Growth of Single Crystal 2D Materials
Based on the above theory of the nucleation and growth of 2D
materials in CVD processes, in this section we will discuss the
relationship between various properties of 2D single crystals and
the CVD growth parameters as well as how to control their
properties by changing these parameters. Specifically, we divide
the controlled growth of 2D materials into seven aspects, i.e., size,
number of layers, orientation, morphology, phase, dopants, and
defects and quality, as illustrated in Figure 3.
3.2.1. Grain Size. The first observation of grain boundaries in
CVD-grown MoS2 was reported by Najmaei et al.65 These grain
boundaries may worsen the electronic, mechanical, and thermal
properties of 2D materials. For instance, charge carrier mobility
in polycrystalline materials would be seriously impaired due to
Figure 3. Schematic showing several key features that need control
during CVD growth of 2D single crystals.
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carrier scattering at the grain boundaries, while such scattering
does not exist in single crystal samples due to a lack of grain
boundaries.66 In another aspect, large area 2D materials are
preferred for fabricating devices based on current silicon-based
semiconducting technology. In addition, compared to small
single crystal samples or large polycrystalline samples, large area
single crystals can provide more active area for photodetectors,
which gives them a high sensitivity and short response time. As a
result, large single crystal 2D materials are preferred for many
applications including high-performance electronics, optoelec-
tronics, flexible and wearable devices, thermal management
applications, etc. Hence, it is of vital importance to design
effective methods to grow large single crystal 2D TMDCs.
Currently, 2D MoS2,67,68 WS2,69 WSe2,70 and MoTe271 crystals
with large grain sizes have been grown.
In the past few years, researchers have devoted much effort
toward this goal and the sizes of 2D materials have been
increased from submicrometers to several micrometers, and at
present even to millimeter or centimeter levels.72−74 To achieve
the growth of large single crystals, a reasonable strategy is to
decrease the nucleation density. Based on this consideration,
Chen et al. have reported simple CVD growth of monolayer
MoSe2 single crystals with a size as large as ∼2.5 mm on molten
glass, as shown in Figure 4a,b. The molten glass at high
temperature forms a very smooth surface, resulting in few
nucleation sites for growing large MoSe2 crystals. A decent field-
effect mobility of 95 cm2 V−1 s−1 and an on/off current ratio of
107 for MoSe2 field-effect transistor (FET) were obtained and
were attributed to the high quality large crystals.75 In principle,
the use of molten glass or, more generally, other liquid or quasi-
liquid substrates may help in the growth of a variety of 2D
materials besides MoSe2. This method certainly needs more
exploration and development to look for other molten substrates.
In addition, additives in the CVD process may have similar effects
in decreasing the nucleation density. By introducing a small
amount of oxygen into the CVD chamber to suppress the
nucleation density by etching away unstable nuclei, large
triangular monolayer MoS2 domains with sizes up to 350 μm
were grown on c-plane sapphire.76 These results exemplify the
positive effects of decreasing the nucleation density to achieve
large size TMDCs.
Another important aspect of increasing crystal size is
maintaining the reaction activity for the material growth over
long time. Decreasing the energy barrier for the reaction should
effectively achieve this goal. A typical example of this idea was
reported by Gao et al.26 According to a self-limited catalytic
surface growth mechanism, large area monolayer WS2 single
crystals were grown on Au foils with sizes up to the millimeter
level. The importance of the Au foil lies in that S2 can dissociate
into two S atoms on Au surface, which results in a lower energy
barrier for the sulfurization of the WO3 precursor. As a result of
this lower energy barrier, high-quality single crystal WS2 domains
have been grown, as shown in Figure 4c,d. In a similar way, large
single crystal MoS2 domains with an edge length of 80 μm were
grown on Au foils.77 In addition, WS2 single crystals with sizes as
large as 135 μm were grown on c-plane sapphire by maintaining
the activity of the lateral growth process a over long time.78
Up to now, the sizes of CVD-grown TMDC single crystals are
still far smaller than those of CVD-grown single crystal graphene.
Understanding the grain boundary formation kinetics,79
decreasing the nucleation density, increasing the growth rate,80
and maintaining long periods of growth deserve extensive further
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Figure 4. Growing large single crystal 2D materials. (a) Optical image of MoSe2 crystals grown on molten glass. (b) LEED pattern of MoSe2 crystal. (c)
Optical image of millimeter-size triangular monolayer single crystal WS2 domains grown on Au foil. (d) Superimposed image of 12 SAED patterns taken
from different parts of the same WS2 domain, confirming it is a single crystal. (a, b) Reprinted from ref 75. Copyright 2017 American Chemical Society.
(c, d) Reprinted with permission from ref 26. Copyright 2015, Rights Managed by Nature Publishing Group.

Figure 5. Controlling the number of layers in 2D materials during CVD growth. (a−c) Optical images of the CVD growth of (a) 1−2 layer, (b) 1−3
layer, and (c) 1−4 layer MoSe2. (d) Atomic configuration, (e) optical image, and (f) HAADF-STEM image of AB stacked bilayer MoS2. (g) Atomic
configuration, (h) optical image, and (i) HAADF-STEM image of AA′ stacked bilayer MoS2. (a−c) Reprinted with permission from ref 31. Copyright
2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (d−i) Reprinted from ref 87. Copyright 2015 American Chemical Society.

investigation to obtain centimeter or even inch size wafer high
quality 2D TMDC single crystals.
3.2.2. Layer. One of the fascinating advantages of 2D
materials is that their properties are tunable by controlling the
number of layers. For the majority of TMDC materials, the band
gap decreases with an increase in the number of layers and this
6097
tendency is much more obvious when a few layers are involved.
Obviously, materials with a tunable number of layers are
desirable for many applications including electronics, optoelec-
tronics, catalysis, and energy applications.81−84 More interest-
ingly, when the layers of TMDCs such as MoS2, MoSe2, WS2, and
WSe2 decrease down to monolayer, there is a transition from
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Figure 6. Controlling the grain orientations of TMDCs during growth. (a) SEM image of aligned WSe2 flakes grown at 950 °C on c-plane sapphire. (b)
AFM image showing initial WSe2 nuclei aligned at sapphire step edges. (c) Atomic models illustrating aligned nucleation of WSe2 on c-plane sapphire.
(d) Schematic showing top view of relative lattice orientations of monolayer MoS2 and c-plane sapphire. (e) Optical image of monolayer MoS2 grains
grown on atomically smooth sapphire; inset, RHEED pattern. (f) Orientation histogram based on the area shown in image e. (a−c) Reprinted from ref
45. Copyright 2015 American Chemical Society. (d−f) Reprinted from ref 92. Copyright 2015 American Chemical Society.

indirect to direct band gaps. This characteristic is responsible for
their potential applications in optoelectronic devices such as
light-emitting diodes (LEDs), laser diodes, and photovoltaic
(PV) devices. Apart from the importance of precise control of the
number of layers for device applications, it is also significant in
using layer-by-layer stacking and designing multifunctional van
der Waals heterostructures, which provide versatility in many
new properties and novel devices. All these opportunities stem
from the number of layers, and it is therefore important to
develop effective means to precisely control this parameter.
To control the number of layers in TMDCs, some effective
approaches have been developed, such as using oxygen-plasma-
treated substrates for one to three layer MoS2 growth.85 In
addition, by controlling the growth temperatures in a one-step
CVD reaction, MoSe2 crystals with a number of layers from one
to four have been grown.31 Specifically, growth at 750, 825, and
900 °C leads to the formation of monolayer, bilayer, and three to
four layer MoSe2, respectively. As shown in Figure 5a−c, the
uniform and atomically smooth surface of MoSe2 crystals with a
well-defined number of layers can be clearly distinguished. In a
similar manner, with an increase of growth temperature, the
number of layers in WSe2 increased with the same tendency.24 By
using different 2D materials such as SnS2, TaS2, and graphene as
substrates, MoS2 crystals with the number of layers tuned from
one to six have been grown by using volatile MoCl5 as precursor
in a typical low-pressure CVD (LPCVD) system, at temperatures
lower than 500 °C.86 Uniquely for these structures, due to the
band structures dependent on the number of layers, the
boundary area between adjacent layers can act as semiconductor
junctions for further advanced device applications.
On the basis of the precise control of the number of layers, the
stacking of the layers may determine the properties of the
materials and consequently their device applications. Specifically,
3R phase TMDC materials with ABC type stacking and
noncentrosymmetric property facilitate their unique applications
in spintronics and valleytronics. Considering the theoretical
predictions of the existence of two different stacking orders for
6098
TMDC materials, i.e., AB order with a 0° twist angle between
adjacent layers and AA′ order with a 60° twist angle, Xia et al.
have grown these two stacked types of MoS2 bilayer crystals by
CVD.87 The different stacking orders are clearly observed by
optical images (Figure 5e,h) and high angle annular dark field
scanning transmission electron microscope (HAADF-STEM)
images as shown in Figure 5f,i. Very recently, Shearer et al.
showed that stacking in WSe2 was controlled by a screw
dislocation driven growth model. The stacking arrangements in
centrosymmetric or noncentrosymmetric styles are strongly
correlated to the number and rotation of screw dislocation spirals
(triangular, hexagonal, or mixed). Importantly, these screw
dislocation spirals can be adjusted by changing the ratio of
precursor Se and WO3 powders in the CVD reactions.88 These
results confirm that the number of layers and the rotation angle
of TMDC layers can be tuned by changing the CVD reaction
conditions.
It is noted that a clear relationship between the number of
layers and rotation angles of 2D materials and their CVD growth
parameters are still not well understood. Instead, most currently
established methods are based more on experience and may or
may not work for other materials or CVD systems. This needs
further study in order to obtain a deep understanding of the
mechanism controlling the number of layers in 2D materials. For
example, it has been demonstrated that the concentrations of
precursors have an important influence on the nucleation
locations of 2D materials, either at the edges or on the surface of
existing layers. This feature would help in controlling the layer
formation during the growth of TMDCs.
3.2.3. Orientation. Controlling grain orientation to obtain
alignment of 2D materials is another important factor in
understanding their nucleation and growth mechanism. On the
one hand, the relative angle between them and the underlying
substrates is a clue to a nucleation model and it provides a novel
way to investigate their nucleation. On the other hand, mis-
oriented lattice growth may lead to the formation of grain
boundaries and defects during the merging of adjacent 2D
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Figure 7. Morphology control of TMDCs. (a) Schematic shows the spatial sectioning of the growth substrate with various MoO3 vapor concentrations
as a function of distance between Mo source and substrate (upper) and corresponding morphologies of the MoS2 grown (lower). (b) Schematic of the
relationships between the Mo:S atom ratios and the domain shapes of MoS2. (a, b) Reprinted from ref 100. Copyright 2014 American Chemical Society.

domains, which would have negative effects on their electrical,
thermal, and mechanical properties. In contrast, it has been
reported in graphene growth that when parallel hexagonal
graphene domains (domains with a 60° rotation) merge, they
form meter-size single crystal graphene.89,90 It is reasonable that
parallel triangular TMDC domains (domains with a 120°
rotation) would merge into a single crystal TMDC in a similar
way. Hence it is very meaningful to control the orientation and
grow well-aligned TMDC domains in order to prepare wafer-
scale single crystalline TMDCs for the fabrication of large-scale
device arrays with few grain boundaries, which would improve
the uniformity and performance of devices significantly.
Recently, researchers have demonstrated that the substrate
plays a key role in the lattice-orientation control of TMDCs
during their growth. The strong van der Waals interactions and
the degree of lattice matching between the substrate and the
grown material determines the orientation preference of the
grown samples. c-plane (0010) facet sapphire is often used as the
substrate for nanomaterial growth because of its high quality
single crystal nature and lattice symmetry considerations.91
Inspired by the principles involved in the aligned growth of
carbon nanotubes, a new step-edge-guided growth method has
6099
been reported to grow aligned WSe2 on a c-plane sapphire
substrate.45 In this approach, the nucleation of WSe2 prefers to
occur along the periodic atomic step/terrace structure on the c-
plane sapphire surface, resulting in a specific orientation and
consequently the aligned growth of WSe2 crystals where one
edge of a WSe2 domain is parallel to a step/terrace direction of
the sapphire substrate, as confirmed by scanning electron
microscopy (SEM; Figure 6a) and atomic force microscopy
(AFM; Figure 6b). Another strategy to control the orientation of
2D crystals is to use an epitaxial relationship between the
substrate and the material. For example, according to the
epitaxial growth of MoS2 on a c-plane sapphire substrate, a
limited number of lattice orientations with lattice rotation angles
θ between the crystallographic axes of monolayer MoS2 and c-
plane sapphire including 0 and 60° as majority orientations and
30 and 90° as minority orientations are clearly demonstrated in
Figure 6d−f.92 This good control over orientations can be
ascribed to the match of the sapphire lattice with MoS2 lattice. In
addition to the sapphire substrate, highly oriented pyrolytic
graphite (HOPG) is another substrate which can help in forming
apparently ordered orientations of MoS2 domains during
growth.93 At this point, it seems that the substrate lattice
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Figure 8. Phase control of TMDCs. (a) Sequential annular dark-field STEM images showing phase transformation of MoS2 at 600 °C. (b)
Corresponding model of atom movements during the 2H−1T phase transition. (c) Schematic of the synthesis of a MoTe2 thin film by two-zone CVD.
(d) Temperature dependent phase evolution of MoTe2 thin films synthesized at different N2 flow rates. (a, b) Reprinted with permission from ref 109.
Copyright 2014, Rights Managed by Nature Publishing Group. (c, d) Reprinted from ref 119. Copyright 2017 American Chemical Society.

structure, especially c-plane sapphire, is relatively efficient in its
ability to adjust and control domain lattice orientations. Other
strategies, such as controlling the gas flow direction and
regulating the growth temperature, could be combined with
the choice of a special substrate, to further improve the alignment
and orientation of 2D materials.
Compared with the control of the crystal size and number of
layers, there are fewer reports about controlling the orientation of
the 2D material grown. Considering the importance of the
orientation in the basic growth mechanism, an understanding of
how to grow large single crystal 2D materials by parallel domains
merging requires more effort. For example, more substrates need
to be explored, including those of single crystal, polycrystalline,
or amorphous metals, and their oxides and nitrides with
engineered surface properties and textures. Of these we need
to pay special attention to single crystal metal substrates because
Au has been shown to be able to grow WSe2 at an ultrafast rate.80
If this could be achieved with the same orientation of each
domain, one could produce fast growth of large single crystal 2D
materials over single crystal metal substrates, which would make
a big contribution to the field. The gas flow direction and
dynamics in the CVD chamber have been shown to influence the
alignment of carbon nanotubes,94−96 but whether the use of such
parameters can be used to control the alignment of 2D materials
is unknown and needs further investigation.
3.2.4. Morphology. Morphology control is important to
understanding the relationships between the structure and
performance of 2D materials in catalysis, sensors, energy
applications, etc. For example, it is argued that the electro-
catalytic activity of TMDC materials toward the hydrogen
6100
evolution reaction (HER) is closely related to the density of edge
sites, suggesting that the morphology can have an important
influence on the catalytic performance.97 From another
perspective, because of the threefold lattice symmetry of
TMDCs, triangular crystals are commonly obtained in CVD
growth. TMDCs with different morphologies, including
dendritic, truncated triangles, three-pointed stars, hexagons,
and six-pointed stars, have also been grown. The morphologies of
as-grown materials are determined by the barrier for edge
diffusion of atoms. When the edge diffusion barrier is high,
attached atoms can hardly find the most favorable binding sites,
leading to the formation of irregular morphologies such as
dendritic.98 Theoretical calculations have shown that the
morphologies and edge structures of MoS2 can be tuned by
changing concentrations of Mo and S species, and these influence
the magnetic and electronic properties of MoS2.99 The shape and
edge structure are largely dependent on the reaction conditions,
such as precursor concentration ratio, substrates used, gas flow
rate, etc., providing an opportunity to study the growth kinetics
of TMDCs in-depth.
According to the basic principles of the theory of crystal
growth, the shape of a crystal is governed by the growth rate of
different crystal facets. In this respect, Wang et al. have
systematically studied the relationship between the mass ratio
of the precursors, and their temperature, and flow rate on the
morphology evolution of MoS2. As shown in Figure 7a, the
MoO3 vapor concentration is related to the distance between the
Mo source and the substrate, providing an effective way of
adjusting the ratio of Mo and S in the reaction. Consequently, the
morphologies of MoS2 show a transformation from medium-size
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truncated triangles to large triangles, and then back to medium-
size truncated triangles followed by decreasing sizes of hexagons,
and finally very small triangles. The reason for these changes is
ascribed to the differences of the growth rates of different crystal
facets of MoS2 (Figure 7b). Specifically, the growth rate of S-zz
terminations and Mo-zz terminations are proportional to their
relative concentrations. Here S-zz termination refers to a zigzag S
edge while Mo-zz refers to a zigzag Mo edge. At high Mo
precursor concentrations, the S-zz termination will be bonded to
Mo atoms to obtain Mo-zz terminated MoS2 triangles.100 This
work provides an effective way to control the morphologies of
TMDCs during CVD growth. When changing the relative
concentrations of Mo and S, the edge features, such as chalcogen-
terminated edges or metal-terminated edges, can be modified.
Based on this report, a generalized TMDC growth theory
considering both thermodynamic and kinetic mechanisms has
been proposed.101 It has also been reported that temperature has
an effect on the shape evolution of WSe2, from triangles and
truncated triangles to hexagons as the temperature is increased
during CVD growth.24 The growth of dendritic shape monolayer
MoS2 has been reported by Zhang et al. that shows a high
catalytic activity in HER.102 These strategies to control the
morphology may also work for other 2D materials such as
graphene and Mo2C in terms of tuning their shapes and edge
structures.103,104
Although several typical morphologies and edges have been
grown and can be controlled well, some novel structures with
complicated shapes such as the symmetric twinned nanoislands
of TMDCs,105 which was predicted in theory recently and may
exhibit intriguing physics properties, have not been grown yet
and further investigations are needed.
3.2.5. Phase. TMDCs have a wide variety of phases, and
phase control is another very important aspect of their growth. In
MX2 which has an X−M−X arrangement with three layers,
where the chalcogen atoms are vertically aligned along the z-axis
(ABA stacking), a trigonal prismatic phase, also called the 2H
phase, is formed with a trigonal prismatic coordination of the
metal atoms. Differently, when the adjacent chalcogen layers shift
toward each other (stacking by an ABC model), an octahedral
phase is formed, also called the 1T phase, with an octahedral
coordination of the metal atoms. Typically, a distorted octahedral
phase (1T′ phase) is often observed, especially for group 7
transition metals.106 Different phases have distinctly different
properties; for example, 2H phase TMDCs are semiconductors
while 1T phase ones are metallic. It is reported that the
semiconductor−metal transition can be correlated to the
stacking sequence of the 1T phase,107 and this feature could
provide a simple way to alter the properties without adding or
removing any atoms. Based on this example, it is of great
importance to directly control the phase produced in the growth
process in order to make it easier to use the material in many
areas.108
Generally, stable phase TMDCs are easy to grow in a typical
CVD system, while the direct growth of metastable phases is
challenging for thermodynamic reasons. Previously, the
structural transformation of monolayer MoS2 (2H to 1T) at
the atomic level has been observed by in situ STEM studies.109
This shows the step-by-step progress (Figure 8a) and the atom
movements (Figure 8b) in MoS2 during such a 2H to 1T phase
transformation. It was noted that an intermediate phase (α
phase) with a band-like structure is necessary to promote this
phase transformation and an electron beam helps the growth of
small 1T phase MoS2 domains.
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Review
Recent research demonstrates that an efficient way to obtain
metastable phase TMDCs relies on post-treatment of the
samples by alkali metal intercalation, 110 electron beam
irradiation,111 plasma treatment,112 mechanical force,113 etc.
Lithium-containing salts, such as n-butyl lithium, are widely used
in the phase engineering of TMDCs.114 Alternatively, by using
the lithium-containing molten salts LiOH and (NH4)2MoS4 as
precursors, Chang et al. have grown 1T phase MoS2 through the
intercalation of lithium ions into MoS2 layers when it was
calcined at a high temperature.115 Although the Li-intercalated
MoS2 1T phase is metastable, recent work by Tan et al. has
demonstrated that hydrogenating the intercalated lithium to
form lithium hydride enhances its stability in air.116
Although metastable phases of TMDCs grown directly by a
CVD reaction have rarely been reported, some important studies
have been made. Previously, bulk MoS2 with the metastable 1T
phase was grown in a CVD system by the sulfurization of
potassium molybdate. It was shown that the potassium
counterions in the as-grown material promote the formation
and stabilization of the MoS2 1T phase.117 In addition, a
metastable 1T WS2 monolayer has been prepared by colloidal
synthesis in nonaqueous solvents.118 The 2H phase or the 1T
phase materials are synthesized by simply controlling the
reactivity of the tungsten precursors and the reaction times.
Very recently, Yang et al. reported a continuous phase
transformation among phases by adjusting the tellurium vapor
mass-transfer (carrier gas flow rate) and tellurization reaction
coefficient (reaction temperature), as illustrated in Figure 8c.119
The relationships between the four phases and conditions are
clearly depicted in Figure 8d, showing that a high gas flow rate
and a low temperature are preferrable for growing 1T′ MoTe2. In
another study, single crystal monolayer 1T′ MoTe2 has been
grown by CVD using ammonium heptamolybdate and tellurium
as precursors and sodium cholate as a promoter in the
reactions.120 Intriguingly, single- and few-layer samples of all
three phases of MoTe2 (2H, 1T, and 1T′) have been selectively
grown by changing the growth and quench temperatures in the
same CVD process.121 These studies indicate that introducing
functional ions or changing the reaction conditions are effective
approaches for phase control, and it is therefore reasonable to
believe that the controlled growth of high quality and metastable
phase TMDC crystals, especially S and Se based, by CVD
methods may be possible in the near future.
3.2.6. Doping. As a supplement to the limited intrinsic
properties of specific 2D materials, elemental doping provides
another approach for tuning the properties. Specifically,
elemental doping has been proposed for modulating the
electronic structures of TMDC materials as well as changing
their physical and chemical properties. Considering the
similarities in the atomic structures of various TMDCs, there is
great potential for making ternary TMDCs with metal dopants
(e.g., MoxW1−xS2) or chalcogen dopants (e.g., MoS2xSe2−2x).
However, because the metal atoms are stacked between adjacent
chalcogen atoms, it may be more challenging to dope metals than
to dope chalcogen atoms in the CVD growth of TMDCs. Equally
importantly, control of the atomic concentration is still difficult
and deserves further study. Nevertheless, CVD growth provides a
promising solution to the control of the concentration and
position of dopant atoms in TMDCs.
A common strategy for preparing ternary TMDC materials is
to introduce a dopant precursor into a CVD system during
material growth. In this way, MoS2xSe2(1−x) materials were grown
by simultaneously putting S and Se precursors into the CVD
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Figure 9. Doping 2D TMDCs. (a) Different phases depending on concentration x in WSe2(1−x)Te2x. (b) Raman spectra of monolayer 2H WSe2(1−x)Te2x
(x = 0−0.6) alloys. (c) Raman spectra of monolayer 1T WSe2(1−x)Te2x (x = 0.6−1) alloys. (d) Optical image and AFM image of as-grown triangular
WxMo1−xS2 flake (left); Raman intensity map and EDX W and Mo elemental maps for as-grown WxMo1−xS2 flake (right). (e) Normalized room-
temperature PL spectra of a single layer MoS2 film after sputtering and DS insertion cycles (left) and DFT-based band gap of MoS2(1−x)Se2x between the
limits of pure MoS2 and pure MoSe2. (a−c) Reprinted with permission from ref 125. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim. (d) Reprinted with permission from ref 128. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Reprinted from ref
131. Copyright 2014 American Chemical Society.

chamber for the reaction. 122,123 Few-layer MoS2x Se 2(1−x)
materials with about 2 wt % Se doping throughout the whole
crystals were grown in a similar way.124 However, this does not
work for less reactive chalcogens such as Te. To tackle this
problem, Yu et al. reported the chemical vapor transport (CVT)
growth of bulk single crystal ternary WSe2(1−x)Te2x followed by
Scotch-tape-based mechanical exfoliation to prepare monolayer
WSe2(1−x)Te2x (0 < x < 1). As shown in Figure 9a, the phase can
be precisely tuned as a function of Te concentration, where x =
0−0.4 for the 2H structure, x = 0.5 and 0.6 for 2H and 1Td mixed
structures, and x = 0.7−1.0 for the 1Td structure. In Figure 9b,c,
the doping concentrations of monolayer WSe2(1−x)Te2x were
measured by the peak shift and sharpness of the two
characteristic E2g and A1g peaks in their Raman spectra.125 In
another respect, monolayer MoS(1−x)Se2x crystals with a large
composition tunnability (x = 0.41−1) and controllable edge
orientations have been obtained in a PVD method.126 Although
the above results show good control of the TMDC phases, the
direct CVD growth of monolayer WSe2(1−x)Te2x crystals is still to
come.
To obtain metal-doped ternary TMDCs, Wang et al. reported
the growth of a Mo1−xWxS2 monolayer by an LPCVD method.
Here a highly volatile precursor, WCl6, was selected as the W
source, MoO3 was used as the Mo source, and the growth
temperature was determined by the reaction of MoO3 with S,
which can be as low as 700 °C. The Mo/W ratio can be tailored
by tuning the concentrations of the MoO3 and WCl6 supplies,
and the chemical composition of the as-grown Mo1−xWxS2
monolayer is homogeneous.127 In a different way, Liu et al.
grew monolayer triangular WxMo1−xS2 crystals with a size of 20
μm using atmospheric pressure CVD.128 The MoO3 and WO3
precursor powders were located separately in the chamber. As
shown in Figure 9d, Raman intensity maps at a frequency of 408
6102
cm−1 and energy dispersive X-ray (EDX) maps of elemental Mo
and W are not uniform across the whole crystal, indicating spatial
segregation of the Mo and W. In a further experiment, using a
mixture of MoO 3 and WO 3 as precursor, monolayer
Mo(1−x)WxS2 was obtained in a one-step CVD process.129
When annealing mixed MoS2/WO3 powders in sulfur vapor,
triangular MoxW1−xS2 monolayers with gradual concentration
profiles of W and Mo have been grown.130 It is reasonable to
believe that if the Mo and W atoms are uniformly distributed,
performance and reproducibility of a device made from the
material would be improved.
Post-treatment of as-grown samples to obtain ternary TMDCs
is another easy and efficient way to dope them. Ma et al. have
grown monolayer MoS2 by a conventional CVD method
followed by the removal of certain sulfur atoms by exposure to
an Ar plasma. Diselenodiphenyl (DS) was then used to insert
selenium atoms into the sulfur vacancies to obtain MoS2(1−x)Se2x
crystals.131 The photoluminescence (PL) spectra in Figure 9e
show evidence for the successful doping of selenium atoms into
the MoS2 crystals, and the composition-based band gap change is
consistent with theoretical predictions. Combining this method
with patterning, it is possible to produce doping at desired
locations, overcoming the limitations in a one-step CVD growth
process and showing potential for device applications.
3.2.7. Quality and Defects. Quality and defect control is
another important aspect of TMDC growth. On the one hand,
high quality TMDCs are highly desired for high performance
electronics and optoelectronics,132 although, unfortunately,
defects and impurities are inevitably generated during their
CVD growth in current growth methods, and these charged
impurities, defects, and traps may seriously degrade charge
carrier mobility.133 On the other hand, a controlled type and
density of defects in TMDCs has effects on the 2D structure itself
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and may be desirable for applications in catalysis, energy storage
and conversion, sensors, etc.134,135 For example, theoretical
calculations show that a line of S vacancies in MoS2 can lead to a
band structure transition from semiconductor to metal,136 and n-
doping high conductivity WSe2 was achieved by creating Se
vacancies through H2/He plasma treatment.137 Therefore, the
control of defect type and density is an important problem that
must be solved. To realize this, defect formation mechanisms in
TMDCs, especially vacancies which are the major defect, need to
be carefully studied. In addition, defect regulation methods and
principles during CVD growth need to be understood and
efficient approaches to the recovery of defects found.
Chalcogen vacancies are the typical defects in TMDCs because
they have the lowest formation energy. Previously, the formation
mechanisms of S vacancies using electron irradiation have been
predicted by density functional theory (DFT) calculations138 and
the relationship between the number of S vacancies and the field-
effect mobility and photoluminescence of MoS2 have been
studied.139,140 For native chalcogen vacancies in few-layer MoS2,
S vacancies on the surface can act as electron donors and induce
localized states in the band gap, which play a key role in the
charge transport by nearest-neighbor hopping or by variable-
range hopping.141 Understanding the influence of defects may
help tune the charge mobility for achieving high performance
devices.
In addition, metal vacancies in TMDCs can influence the
macroscopic material properties. The metal vacancies with deep-
trap states have a more serious effect on the electron mobility and
photoluminescence than that of chalcogen vacancies with
shallow-trap states. Jeong et al. have grown hexagonal WS2
monolayer by a CVD method using ammonium metatungstate
hydrate as liquid W precursor and sodium cholate hydrate as a
promoter in a convention CVD system.42 The S vacancy
domains and W vacancy domains, in triangular shape,
alternatively coexisted within the hexagonal WS2 layer. This
unique defect arrangement was well-characterized by PL
intensity and STEM images. The metal vacancies are formed
because of the tungsten concentration variation at certain
conditions.
To recover these defects, post-treatment is another effective
way. Yu et al. have developed a thiol chemistry method to repair
sulfur vacancies in MoS2 by (3-mercaptopropyl)trimethoxysilane
treatment. After repair, the MoS2 devices show enhanced
electron mobility because of the reduction of charged impurities
and short-range scattering.142 For selenium-based TMDCs, Han
et al. used hydrohalic acid to reduce the Se vacancies and
suppress the trap states, and increased the photoluminescence
intensity by a factor of 30.143 For the recovery of these chalcogen
vacancies, the recombination kinetics of exctions before and after
repair by organic molecules are also investigated by transient
optical characterization.144 Different from the above methods, Lu
et al. used oxygen to fill the chalcogen vacancies by a focused laser
beam treatment in ambient conditions.145 These results
demonstrate that proper chemical treatment is efficient in
removing the point defects and degrade the traps in TMDCs.
Moreover, the in situ introduction of additives to the CVD
reaction systems may serve as another simple way to repair
defects in TMDCs during growth. As shown by Zhou et al.,
molecular sieves were used to trap the precursors of the
byproduct during MoTe2 growth.146 This approach can be
developed further; for example, some additives may fill vacancies
in the crystal lattices of TMDCs to obtain a crystal without
vacancies.
6103
Review
4. CVD GROWTH OF WAFER-SCALE CONTINUOUS 2D
MATERIAL FILMS
In section 3, we talked about the controlled growth of TMDCs
with emphasis on the properties of the individual domains,
including their grain size, number of layers, orientation,
morphology, phase, doping, and defects. In this section, we will
focus on how to grow large, continuous, and homogeneous films
of 2D materials, because the preparation of such wafer-scale
uniform samples is a prerequisite for their practical use. We focus
on two key questions in this regard. The first is how to develop
methods for growing wafer-scale uniform 2D films by CVD, and
the second is how to achieve low temperature growth of 2D
continuous films on flexible and transparent substrates, which are
usually unable to withstand high-temperature processing.
4.1. Motivation for and Challenges of Growing Wafer-Scale
Continuous and Homogeneous 2D Material Films
Wafer-scale, continuous films of 2D materials that are compatible
with the current silicon-based microfabrication processes are
greatly needed for applications in electronic and optoelectronics.
By patterning the large area 2D films into arrays, batches of
devices could be fabricated on a single substrate technologically
relevant scale. Ideally, the as-prepared films should be
homogeneous over the entire substrate to guarantee structural
and electrical uniformity of all the devices in these arrays.
Although alternative approaches such using solution-processed
2D materials in spray coating or in an inkjet printer are capable of
fabricating FETs covering large area substrates, the performance
of these devices is relatively poor (with a charge carrier mobility
of around 0.1 cm2 V−1 s−1 and an on/off current ratio of 600).147
Therefore, direct CVD growth of continuous and high quality 2D
films over large areas is urgently needed for them to be used in
electronic devices.
The key challenges in growing high quality wafer-scale film are
as follows. (i) The first challenge is the growth of a continuous
film with large grain. Small grains are necessarily accompanied by
a high density of grain boundaries, increasing the scattering of
carriers and consequently degrading the electronic properties of
the films. (ii) The present uniformity of as-grown films is not
great. Growth at different areas may vary and layer distribution
may be random, both of which hinder the scalable fabrication of
device arrays. (iii) Transfer of 2D films from growth substrates to
target ones is usually tedious and difficult to scale up. The transfer
process is unavoidable for specific applications, while the damage
and contamination introduced during transfer is more serious for
large area films than for an individual flake. (iv) The mass
production of continuous films remains a major challenge. The
slow growth speed and strict growth condition requirements still
limit the scalable production of large area 2D materials. In section
4.2, we discuss the progress made in solving these challenges in
recent years.
4.2. Growth of Continuous 2D Films on Rigid Substrates
To overcome the above challenges, researchers have devoted
extensive efforts to growing high quality continuous films by
modified CVD methods, such as MOCVD, LPCVD, ICP-CVD,
the predeposition of metal or metal oxide films,148 and thermal
decomposition of precursors such as (NH4)2MoS4, etc. The main
achievements in the growth of wafer-scale continuous films are
given in Table 1, and are discussed in sections 4.2.1, 4.2.2, and
4.2.3.
4.2.1. MOCVD Method. Metal−organic precursors are very
attractive for the controlled growth of large area TMDC
materials because they can be fed into the CVD chamber in
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 Table 1. Summary of Growth of Continuous Films of TMDCs by Various Methods
methods materials/substrates size of films growth parameters device performance ref
Metal−Organic CVD Method
MOCVD monolayer MoS2, 4-in. wafer 0.01 sccm Mo(CO)6/W mobility: 30 cm2 V−1 s−1 at room temp, and 114 cm2 V−1 s−1 at 90 K 25
WS2/silicon scale; grain (CO)6; 0.4 sccm
size ∼1 μm (C2H5)2S; 5 sccm H2;
150 sccm Ar; 7.5 Torr,
Chemical Reviews

550 °C; 26 h
Conventional CVD Method
vapor reaction monolayer MoS2 wafer scale; 35 mg of MoO3; 600 mg of 7 cm2 V−1 s−1 67
method grain size sulfur; 750−800 °C; 130
20−1000 sccm Ar; 0.67 Torr
nm
vapor reaction MoSe2 2 × 2 cm2; 300 mg of Se; 20 mg of 42 cm2 V−1 s−1; on/off ratio: 106 152
method grain size MoO3; Si/SiO2; 750 °C;
0.3−0.7 mm 20 min; H2/Ar (15%) 75
sccm
vapor transport monolayer (few 1 cm2 WSe2 powder, 1060 °C for p-type behavior, hole carrier mobility of 100 cm2 V−1 s−1 (monolayer), 350 cm2 V−1 s−1 (few layer) 153
layer), WSe2/SiO2/ source T, 765 °C for
Si substrate T, 100 sccm, 40
min
Thin Film Deposition Method
thermal deposi- MoS2/c-plane sap- 2-in. wafer MoO3 film deposition on/off current ratio: 105; electron mobility 0.8 cm2 V−1 s−1 154
tion phire scale; tri- method; Ar/H2 (4:1), 1
layer Torr, 500 °C, 1 h; sulfur,
1000 °C, 30 min, 70 sccm
Ar, 600 Torr

6104
electron-beam 1T′ MoTe2/SiO2/Si wafer scale 1 nm Mo/MoO3 film by sheet resistance of the film is 1120 Ω sq−1, sheet resistance of Hall bar devices is 1900−2028 Ω sq−1 157
deposition film; 3.1 nm electron beam evapora-
thickness tion; Te with molecular
sieves, 3 sccm Ar + 4
sccm H2, 700 °C, 1 h;
atmospheric pressure
magnetron sput- MoS2/SiO2/Si wafer scale MoO3: RF magnetron mobility of ∼21 cm2 V−1 s−1 (bilayer) and ∼25 cm2 V−1 s−1 (trilayer), on/off ratios in the range of ∼107 (bilayer) and 104−105 (trilayer) 158
tering continuous sputtering at 300 °C;
film (1 cm sulfurization at 650 °C for
× 9 cm); 1 h, 100 sccm Ar,
bilayer, tri- 2 × 10−2 Torr
layer, few
layers
PLD MoS2/various sub- size up to PLD targets: MoS2/S ratio: electrical resistivity: 1.5 × 104 Ω cm−1 159
strates substrate 1:1, particle size: S(20
scale, bi- μm), MoS2 (43 μm, 2
layer μm); deposition T:
700 °C
ALD MoS2/Al2O3 wafer scale Mo(NMe2)4 and H2S in none 160
with layers THF, ALD at 60 °C;
adjusted sulfurization in sulfur
vapor at 1000 °C for 5 h
dip coating MoS2/SiO2/Si wafer scale, 1.25 wt % (NH4)2MoS4 in on/off current ratio: 1.6 × 105, carrier mobility: 6 cm2 V−1 s−1 162
trilayer DMF, pull rate of 0.5
MoS2 film, mm/s, sulfurization at
crystal do- 500 and 1000 °C, 1 Torr,
mains larger Ar/H2 = 4:1
than
Review

160 nm

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Chemical Reviews Review

precise amounts that can be controlled to be constant over a long

164
ref time. Using this method, WSe2 monolayer and few-layer films
with a domain size of 8 μm have been grown by MOCVD with
W(CO)6 and (CH3)2Se as precursors.149 In a recent break-
through, Kang et al. used gas-phase Mo(CO)6, W(CO)6, and
(C2H5)2S as precursors and H2/Ar as carrier gas, and grew
continuous 4-in. wafer-scale, homogeneous MoS2 and WS2 films
(Figure 10a,b).25 The growth was found to follow a layer-by-layer
growth mode. From the MoS2 film, a wafer-scale batch of 8100
high performance MoS2 FETs with a global back gate was
fabricated by photolithography (Figure 10c). More practically,
two stacked MoS2 FETs were fabricated at vertical levels on
silicon wafer with the external deposition of 500 nm SiO2
dielectric layers in between. The transfer curves from both
types of FETs show back gate dependent conductance changes,
indicating that their semiconducting behavior is as expected in
MoS2 (Figure 10d). All the above processes demonstrate the
good compatibility of wafer-scale 2D films with conventional
device performance

fabrication procedures, which can be further developed into

three-dimensional structures for scalable device fabrication.
Because of the easy control of reaction parameters and the
constant concentration of each precursor, MOCVD using vapor-
phase precursors has great potential for the production of high
quality and uniform TMDC films.
high photocurrent durability when bending for 105 cycles

4.2.2. Conventional CVD Method. Normally, a combina-

tion of MoO3 (WO3) and S (Se) powders, or WSe2 (MoS2)
powders, serves as the precursors for CVD growth of TMDCs.
Flexible and Transparent Substrate

Single crystals with defined domain sizes are commonly grown in

such setups. By increasing the growth time, TMDC continuous
films can be grown.150 Zhang et al. reported the use of LPCVD
for the scalable growth of polycrystalline monolayer MoS2 films
on Si/SiO2 substrate, using MoO3 and S as precursors.67 The film
is composed of individual domains with sizes ranging from 20 nm
to 1 μm that have coalesced and was used to fabricate FETs with
a back gate. They show a relatively decent mobility of 7 cm2 V−1
s−1 and an on/off current ratio of 106. In another work, by
selective growth at the gap between two stacked substrates, a
continuous monolayer MoS2 film as large as a few square
centimeters was obtained.151 In addition, MoS2, MoSe2, and WS2
films have been grown in a similar way. Gong et al. used MoO3
1.25 wt % (NH4)2MoS4 in

30 min, 450 °C 30 min;

ethylene glycol; 280 °C

and Se as precursors and achieved wafer-scale growth of

growth parameters

continuous MoSe2 films with a controlled number of layers

H2/N2 100 sccm;

and few defects, by tuning the flow rate, growth temperature, and
H2 content during CVD growth. The wafer-scale films led to a
relative high mobility of 42 cm2 V−1 s−1 for back gate MoSe2
1.8 Torr

FETs.152 In addition, large area (1 cm2) atomically thin

continuous WSe2 films have been grown using WSe2 powder
as precursor in a simple growth process.153 For these kinds of
size of films

growth systems, the continuous films are often polycrystalline

grain size:
wafer scale;

and are formed by the merging of numerous individual domains.

N/A

4.2.3. Thin Film Deposition Method. Another general

strategy to grow wafer-scale continuous 2D films is the
materials/substrates

sulfurization (or selenization) or decomposition of predeposited

films (Mo or W foil, MoO3 or WO3 or their salts). There are
MoS2/polyimide

many ways to carry out the predeposition process, such as

thermal deposition, electron beam deposition, atomic layer
Table 1. continued

deposition, magnetron sputtering, and spin-coating method.

For example, to grow wafer-scale MoS2 thin films, a MoO3
precursor with the desired thickness was thermally deposited on
thermal decom-

the (0001) surface of a sapphire substrate. Then, a postannealing

methods

process at 500 °C in a hydrogen atmosphere and sulfurization at

position

1000 °C in sulfur vapor were used to achieve the growth of MoS2

over a 1 × 1 cm2 substrate.154 In another study, Kong et al.
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Chemical Reviews Review

Figure 10. MOCVD growth of wafer-scale continuous 2D material films. (a) Diagram of MOCVD growth setup. Precursors were introduced using
individual mass flow controllers. (b) Photographs of monolayer MoS2 andWS2 films grown on 4-in. fused silica substrates. The left halves show the bare
silica substrate for comparison. (c) Batch-fabricated 8100 MoS2 FET devices on 4-in. Si/SiO2 wafer. Top inset: enlarged image of one square containing
100 devices. Middle and bottom insets: corresponding color maps of δ at gate biases VB = +50 V and −50 V. (d) Diagram of fabrication of MoS2 device/
SiO2 stack by alternating MOCVD growth. SEM image of MoS2 FET arrays on first and second layers. ISD−VSD curves measured from two neighboring
devices on first and second layers of MoS2 FETs. Reprinted with permission from ref 25. Copyright 2015, Rights Managed by Nature Publishing Group.

reported that large areas of vertically aligned MoS2 or MoSe2
layers were grown from an electron beam deposited Mo film
followed by conventional sulfurization or selenization in a typical
CVD system.155 The thickness of the electron beam deposited
Mo films can be tuned, resulting in a good control of the number
of layers in as-grown MoS2 or MoSe2. By using this method,
wafer-scale MoS2 films156 and 2H as well as 1T′ phase MoTe2
continuous films157 have been obtained. Radio frequency
magnetron sputtering was also used to deposit an MoO3 film
followed by sulfurization at 650 °C to prepare MoS2.158 The
thickness of the MoS2 film can be tuned in atomic scale by the
sputtering time, and the fabricated MoS2 FETs show a high
charge carrier mobility and a high on/off current ratio, which are
dependent on the MoS2 thickness. Pulsed laser deposition
(PLD) is another effective approach to deposit thin films for 2D
material growth. In a recent study, a large area MoS2 film with a
controlled number of layers ranging from 1 to 10 was deposited
by controlling the target composition, MoS2, and sulfur particle
size in the target, and other PLD deposition parameters. It is
noted that no additional sulfurization step was required.159
Atomic layer deposition (ALD) is a very powerful method to
grow atomically thin coatings on different substrates. Very
recently, MoS2 films were synthesized at a temperature as low as
60 °C in an ALD system by using volatile Mo(NMe2)4 and H2S
as precursors. The growth rate of MoS2 was 0.12 nm/cycle,
which makes the number of layers and thickness control of MoS2
very precise.160 It is reasonable to argue that this Mo(NMe2)4
precursor can also be used in a MOCVD system for the scalable
preparation of 2D TMDCs. Also, wafer-scale WS2 nanosheets,
whose number of layers could be systematically controlled, were
synthesized by the sulfurization of an ALD WO3 film.161 Besides
the above-mentioned thin film deposition techniques, dip
coating or spin coating is a relatively simple way to prepare
uniform thin films of precursors on a substrate. For example,
(NH4)2MoS4 was dissolved in dimethylformamide (DMF) to
obtain a 1.25 wt % solution and a silicon wafer was immersed into
the solution and slowly pulled out to form a thin (NH4)2MoS4
6106
film on its surface. Then, a two-step annealing process was used
to decompose and convert the (NH4 ) 2MoS 4 into MoS 2
continuous films.162 A similar strategy with a (NH4)2MoS4 film
deposited by spin coating was later reported with atomically thin
and wafer-scale MoS2 layers.163 For these predeposition
methods, the size, the number of layers, and the quality of the
films heavily depend on the deposition condition.
4.3. Growth of Continuous 2D Films on Flexible Substrates
Flexible electronic and optoelectronic devices, wearable sensors,
and other portable devices have great potential in next generation
roll-up displays, electronic paper, electronic skin, etc. Flexible
electronics is an area where 2D materials may surpass silicon due
to their good mechanical properties. For flexible devices, a variety
of polymers are commonly used as substrates, such as polyester
(PET), poly(ethylene napthalate) (PEN), poly(ether sulfone)
(PES), and polyimide (PI). To fabricate device arrays on the
flexible substrates, a continuous film is a prerequisite. Generally,
direct growth and postgrowth transfer are two widely used
methods to prepare continuous films on flexible substrates.
4.3.1. Direct Growth on Flexible Substrates. Flexible
substrates are usually polymeric-based and have a low processing
temperature, high surface roughness, and low thermal expansion
coefficient, making them not preferred substrates for conven-
tional high temperature CVD growth. However, researchers have
developed effective ways to solving these problems. Modification
of the substrate can play a key role in lowering the growth
temperature for 2D materials. Using alloy substrates with low
melting points and the formation of a liquid surface at reaction
temperatures can promote the growth of TMDC continuous
films. For example, Zhou et al. used PI-supported gallium or a
eutectic indium−gallium alloy as the substrate, and synthesized
large area high quality GaSe or GaxIn1−xSe2 films at a growth
temperature as low as 100 °C.165 In this reaction, the alloys serve
as both precursors and substrate with a liquid surface. In
principle, if the correct Mo- or W-containing eutectic could be
found, it would be easy to achieve the direct growth of TMDC
films on flexible substrates. Also, Ling et al. showed that loading
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Chemical Reviews
Figure 11. Direct growth of continuous 2D material films on flexible polymeric substrates. (a) Schematic of temperature−time profile for two-step
thermal decomposition process for synthesis of large-scale, continuous MoS2 layers and thermogravimetric analysis (TGA) of (NH4)2MoS4. (b)
Photograph of homogeneous MoS2 films synthesized directly on PI substrate. (c) Photocurrents of MoS2-based visible-light photodetectors recorded at
P = 12.5 mW cm−2 and V = 20 V before and after bending. Reprinted with permission from ref 164. Copyright 2016 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
specific organic molecules onto the substrates to lower the CVD
reaction barrier and achieve low temperature growth is a
potential method to achieve the direct growth of TMDCs on
flexible polymeric substrates, that the use of PTAS as a promoter
can decrease the temperature for MoS2 growth to 650 °C.166
Nevertheless, there are only a few reports on this technique, and
suitable organic molecules deserve further exploration.
Recently, the thermal decomposition of molybdenum salt,
such as (NH4)2MoS4, has appeared to be an efficient way of
obtaining MoS2 continuous films at relatively low temperatures.
For example, Lim et al. reported a modified two-step thermal
decomposition process for preparing wafer-scale, homogeneous
MoS2 films at low temperatures on a plastic PI substrate.164 In
Figure 11a, intermediate MoS3 was first formed at 280 °C,
followed by decomposition at 450 °C to grow MoS2 continuous
films. A flexible MoS2-based visible light photodetector was then
fabricated on the PI substrate and showed good stability of the
photocurrent after bending to a radius of 5 mm for 105 cycles
(Figure 11b,c). This strategy provided an easy way to directly
grow 2D films on a flexible substrate. However, this
decomposition temperature is still too high for many flexible
substrates. Some volatile additives may be added to the
(NH4)2MoS4 solution to lower the decomposition temperature
to achieve MoS2 growth at even lower temperatures.
4.3.2. Postgrowth Transfer 2D Materials onto Flexible
Substrates. The direct growth of 2D films on flexible substrates
is challenging, and from a more practical aspect, a highly efficient
transfer method is necessary to obtain 2D continuous films on
flexible substrates. Previously, different from a conventional
polymer (PMMA) assisted etching method, Gao et al. developed
a face-to-face transfer method and achieved the wafer-scale
transfer of graphene films.167 The nascent gas bubbles and
capillary bridges between the films and the substrate promote the
detachment of as-grown graphene. For TMDC films grown on
metal substrates such as Au foil, this face-to-face method should
work as well. Recently, Phan et al. reported a direct one-step
method for transferring MoS2 films grown on sapphire or SiO2/
Si substrates to a flexible and transparent PET substrate by using
epoxy glue as a mediator without any etching process.168 For the
6107
Review
growth substrate/MoS2/glue/PET stacked substrate, the flexible
MoS2/glue/PET layer could be easily separated from the growth
substrate, and MoS2 films with size up to 2 cm × 10 cm were
successfully transferred onto PET without any obvious
deterioration of their properties. These high efficiency transfer
methods will accelerate the applications of 2D materials in
flexible devices. Currently, such transfer methods are usually
manual and the development of automatic or semiautomatic
methods is important to increase the yield and efficiency of the
process.
5. CVD GROWTH OF 2D MATERIAL BASED
HETEROSTRUCTURES
Along with extensive research and the rapid development of 2D
materials consisting of graphene, h-BN, TMDCs, phosphorene,
etc., 2D material based heterostructures have recently emerged as
a new research frontier for condensed matter physics and
materials science. From structure and materials points of view,
heterostructures provide additional ways to design and prepare
novel materials with more than one building block. From a
physics perspective, heterostructures provide interesting plat-
forms to exploit new physics as well as investigate the coupling
between elementary particles in different building blocks.169
These 2D material based heterostructures exhibit new physics
related to electron−electron coupling and electron−phonon
coupling, originating from the layer−layer interactions.170
Furthermore, such heterostructures may deliver improved device
performance compared with the separate building blocks.169,171
The energy band alignment and charge carrier mobility in these
heterostructures can be tuned by selecting the components in the
heterostructures, to satisfy different application requirements.
Hence, by precisely designing the components used to build the
heterostructure and sequences in which they are arranged, one
could open up countless opportunities to create new materials
and systems aimed at high-performance device applications.172
Generally speaking, there are two types of 2D material based
heterostructures. The first is vertical heterostructures, where
different 2D materials are stacked layer by layer vertically with no
strong interaction between them, while the second is lateral
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heterostructures, where different 2D materials are seamlessly

174

175

176
174

177

178

179

180
ref
joined to each other, usually by covalent bonds, in the same
plane. For vertical 2D heterostructures, the interlayer interaction

triangular geometry thickness of 0.8 nm

interface transition in scale of ∼40 nm
triangular MoS2 and WS2; type II band

WS2−MoS2 interface roughness is four

monolayer MoS2, Bi2S3: diameter 0.12

junction depletion width is ∼320 nm,
monolayer layer MoS2 at top; weak
is mainly by van der Waals forces (they are sometimes called van

monolayer graphene film at bottom;

interface boundary with width of

unit cells with a width of 15 nm

zigzag oriented boundaries; sharp

der Waals heterostructures), and there is no or little requirement

with whole sizes up to 200 μm2

for lattice matching between the different layers. Because of this,

characterization
several methods have been developed to fabricate such vertical

type II band alignment

heterostructures, including (i) Scotch-tape-based mechanical

μm, length 7.3 μm

exfoliation and multiple step aligned transfer,173 (ii) sequential

n-doping level
deposition of 2D material solutions, (iii) one-step or multistep

alignment
CVD growth, and (iv) some combination of these methods (e.g.,

0.5 nm
exfoliation a 2D material followed by CVD to grow another 2D
material on top). In contrast, lateral 2D heterostructures usually
require atomic level sharpness at the junctions between the

step 1: 0.6 g of WO3 260 °C (Se), Ar/H2 (90/6 sccm) 20 Torr, 925 °C, 15 min; step 2: 0.6 g of MoO3 190 °C (Se), Ar (70 sccm) 40 Torr, 755 °C,
Ni−Ga/Mo foil substrate, NH3−BH3 (110−130 °C), Ar/H2 75 sccm, 30 min, 1000 °C; 4 sccm H2S precursor, 680 °C, 25 min, 10 sccm Ar
one-step CVD: 10 mg of W + 100 mg of Te, 25 mg of MoO3, 500 mg of S; Si/SiO2 (285 nm); 100 sccm Ar; 850 °C, 15 min; atmospheric

one-step CVD: 10 mg of W + 100 mg of Te, 25 mg of MoO3, 500 mg of S; Si/SiO2 (285 nm); 100 sccm Ar; 650 °C, 15 min; atmospheric
materials on each side. These strict requirements make the

graphene: Cu foil, APCVD, 1050 °C, Ar/H2 (930/60 sccm) CH4 20 sccm hydrogen etch graphene BN: NH3−BH3, 120 °C, 10−30 min
graphene: Au foil, AP, CH4 1.5 sccm, H2 30 sccm, Ar 200 sccm, 970 °C MoS2: MoO3(530 °C), S (102 °C), substrate (680 °C), Ar/H2
bottom-up approach, especially CVD growth, one of the most
suitable choices that can be used to grow lateral 2D
heterostructures. In the following sections, recent progress and
achievements on the preparation of both vertical and lateral 2D
heterostructures are presented. Moreover, heterostructures
consisting of 2D materials and LD materials (e.g., 1D nanowires
and nanotubes, 0D quantum dots (QDs)), which we call xD/2D

0.7 g of MoO3, 0.4 g of S, 0.6 g of Se, 750 °C for sulfurization, 700 °C with 5 sccm H2 for selenization, 15 min
heterostructures, have recently attracted increasing attention, are
also highlighted. Although reports of CVD-grown heterostruc-
tures are not as plentiful as those concerned with Scotch-tape-
based exfoliation and aligned transfer ones, the high yield and
comparable high quality make CVD-grown heterostructures
promising for practical applications. Hence, this section mainly
focuses on heterostructures where CVD growth is involved in
their preparation and Table 2 is a summary of the typical
examples of these three kinds of heterostructures, which will be
discussed in detail in section 5.1, section 5.2, and section 5.3.
methods

Bi2S3 and MoO3 mixed powder, 0.5−1 g of S, 20 sccm N2, 650 °C, 6 min
5.1. Vertical 2D Heterostructures
Due to the existence of abundant 2D materials with different
electronic properties and weak requirements of a lattice match
for stacking them together, there are unlimited combinations in
2D vertical heterostructures. Currently, the CVD-based method
Table 2. Summary of Representative CVD Grown 2D Heterostructures

can grow four main types of 2D vertical heterostructures,

including (i) metal/semiconductor junctions consisting of
graphene/s-TMDCs, m-TMDC/s-TMDCs, graphene/phos-
phorus, etc.; (ii) semiconductor/semiconductor junctions
consisting of different s-TMDCs or s-TMDCs/phosphorus;
(iii) semiconductor/insulator junctions consisting of s-TMDCs/
h-BN; and (iv) metal/insulator junctions consisting of
graphene/h-BN, where s-TMDCs and m-TMDCs refer to
semiconducting and metallic TMDCs, respectively. In addition,
complicated heterostructures which are made of more than two
stacked materials are also reviewed in this section.
(50/5 sccm)

5.1.1. Metal/Semiconductor. Graphene/TMDC-based

15 min

metal/semiconductor vertical heterostructures are very impor-

tant because they take full advantage of both graphene with its
high transparency, high conductivity, and tunable work function,
and TMDCs with a wide choice of compositions and band gaps.
graphene/BN
MoS2/MoSe2
MoS2/WSe2
MoS2/h-BN

Bi2S3/MoS2
materials
MoS2/WS2

MoS2/WS2
graphene

As a result, these heterostructures demonstrate interesting

properties in electronic and optoelectronic devices.181−183
MoS2/

For example, high performance electronic devices,184 a

photoresponsive memory,185 biological sensors,186 and flexible
heterostructures

heterostructures

heterostructures

transparent devices183 have been fabricated by stacking the

mechanical exfoliated graphene and TMDC monolayers into
type

heterostructures that clearly point out the advantages of these

xD/2D
vertical

lateral

materials in electronic and optoelectronic applications. Consid-

ering the fact that Scotch-tape-based exfoliation and aligned
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Figure 12. CVD growth of graphene/TMDC based metal/semiconductor and TMDC/TMDC based semiconductor/semiconductor vertical
heterostructures. (a) SEM image of as-grown MoS2/graphene vertical heterostructures on Au foil. (b) Large area STM image (1.11 V, 0.20 nA, 78 K;
44.0 × 44.0 nm) of MoS2/graphene. (inset) Corresponding SEM image. (c) Atomic resolution STM image (0.81 V, 0.23 nA, 78 K; 3.2 × 3.2 nm) of
MoS2/graphene. (inset) Corresponding FFT pattern. (d) Schematic of the three types of heterostructures. (e) Schematics showing monolayer MoSe2
used for WSe2 growth and stack 1 and stack 2 WSe2/MoSe2 heterostructures with corresponding optical images. (a−c) Reprinted with permission from
ref 175. Copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Reprinted from ref 195. Copyright 2015 American Chemical Society.

transfer methods are time-consuming and are only suitable for
individual devices, the development of CVD-based methods to
prepare heterostructures is very important. In an early study, Shi
et al. used a two-step CVD method to grow graphene/MoS2
vertical heterostructures.187 In this work, they first grew
multilayer graphene by CVD and later used it as the substrate
for (NH4)2MoS4 deposition and decomposition to prepare
graphene/MoS2 heterostructures. In another study, a CVD
method was used to first grow a complete monolayer of graphene
on an Au foil, followed by the growth of monolayer MoS2 on top
of graphene. An SEM image of the graphene/MoS2 hetero-
structures is shown in Figure 12a. The high quality of the
materials was confirmed by atomic resolution scanning tunneling
microscopy (STM) imaging (Figure 12b,c). We note that,
although the sizes of graphene and MoS2 domains are large, the
overlapped area between them, i.e., the heterostructures, is
small.175 Similarly, vertical heterostructures made of graphene/
MoS2 nanoribbons were grown by two individual CVD
processes, and showed a high photoresponsivity to visible
light.188 It should be noted that all current heterostructures have
only been formed in small areas and the wafer-scale CVD growth
of vertical heterostructures has not been reported.
5.1.2. Semiconductor/Semiconductor. Due to their wide
range of band gaps and electronic affinities, the stacking of
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different TMDCs can form three types of heterostructures
(Figure 12d). Type I heterostructures are called straddling
heterostructures because the valence band maximum and
conduction band minimum of one material fall within the band
gap of the other. Type II heterostructures, staggered
heterostructures, are where the valence band maximum occurs
in one material while the conduction band minimum is in the
other. In this instance the electrons and holes are confined in two
separate materials, which may result in excellent performance in
optoelectronic device applications. Type III heterostructures,
broken-gap heterostructures, are where the conduction band
minimum in one material is lower than the valence band
maximum in another material, indicating that the valence band
and conduction band overlap at the interface. Compared with
single layer TMDC materials, these 2D material based
heterostructures with different band alignments provide addi-
tional freedom and unique properties in electronic and
optoelectronic devices.189,190
The most straightforward way to prepare layer-by-layer
heterostructures is stacking the as-grown individual TMDCs by
traditional transfer methods. For example, monolayer MoS2/
WSe2 heterostructures were stacked by transferring flakes of one
material onto a flake of the other using a PMMA assisted
method.191,192 A similar method was used to assemble MoS2/
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Figure 13. CVD growth of TMDC/h-BN based semiconductor/insulator vertical heterostructures. (a) Schematic showing preparation of TMDC/h-
BN heterostructures. (b) SEM image of directly grown single crystal MoS2 on h-BN. (inset) MoS2 crystal with a grain size up to 200 μm2. (c) TEM
characterization of MoS2/h-BN heterostructures. (inset) SAED patterns corresponding to heterostructures. (d) Photoluminescence performance of
directly grown and transferred TMDC/h-BN heterostructures. Reprinted from ref 176. Copyright 2016 American Chemical Society.
WS2 vertical heterostructures. For both vertical and planar
devices, they exhibit novel rectifying and bipolar behavior, a high
on/off current ratio, and a high mobility.193 It is shown that this
stacking method is able to fabricate TMDC/TMDC hetero-
structures with relatively good properties.
However, contamination caused by trapped impurities or
residue at the interface and mechanical damage during the
transfer process may seriously modify the intrinsic electronic
properties of each individual material and consequently the
properties of the heterostructure. In addition, it is very difficult to
achieve the large-scale production of TMDC/TMDC hetero-
structures using such an aligned transfer method. Intriguingly, a
one-step CVD growth approach has been demonstrated as being
able to grow this kind of heterostructure, as demonstrated by
Gong et al. for the growth of MoS2/WS2 in 2014.174
Furthermore, sulfurization of deposited Mo and W stacks,
which served as seed layers, was used to grow MoS2/WS2 vertical
heterostructures.194
However, the one-step method has limitations in the spatial
and size control of the heterostructures. Gong et al. discovered a
new two-step CVD method for growing WSe 2 /MoSe 2
heterostructures, where MoSe2 was grown in the first step,
followed by epitaxial growth of WSe2 along the edges and on top
of the MoSe2.195 The sizes of both the MoSe2 and WSe2 could be
easily adjusted, providing a powerful way to control the size of
heterostructures, which reached a size of 169 μm. As shown in
Figure 12d, heterostructures with bilayer WSe2 and bilayer
WSe2/MoSe2 at the edges (stack 1) and vertically stacked WSe2/
MoSe2 heterostructures with an additional WSe2 monolayer and
bilayer at the edges (stack 2) are clearly observed. However, the
edges of these large vertical heterostructures are not clean, and
more effort must be devoted to passivating the edge sites and
activating the top surface of the bottom layers. For periodic
patterns of MoS2/WS2 vertical heterostructures, WO3 and MoO3
were predeposited separately, followed by a thermal reduction
sulfurization process.196 More interestingly, a two-step temper-
ature mediated strategy was used to grow A−A stacked MoS2/
WS2 or A−B stacked WS2/MoS2 vertical heterostructures
without cross contamination of Mo and W atoms.197
In addition to the TMDC/TMDC heterostructures, other
metal chalcogenide materials (i.e., GaS, InSe, SnS2) and metal
halide materials (i.e., CdI2, PbI2) have been the focus of
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considerable interest. Recently, CdI2 nanoplate/TMDC (i.e.,
MoS2, WS2, WSe2) vertical heterostructures were prepared by an
all-CVD approach. The single CdI2 crystals show hexagonal and
triangular morphologies with sizes of 2−10 μm and a thickness of
5−220 nm.198 This new heterostructure design will help to
expand the family of 2D material based heterostructures and
enable new device functionalities.
Black phosphorus (bP) has a high theoretical charge carrier
mobility of up to ∼10 000 cm2 V−1 s−1 and a direct band gap of
about 0.3 eV in the bulk form. In addition, bP FETs typically
exhibit ambipolar behavior with the p-branch stronger than the
n-branch. These features make bP a good complement to most
TMDC materials which are n-type semiconductors and have
band gaps in the visible light range. Hence, the assembly of bP
with TMDCs can produce van der Waals p−n heterostructures
as building blocks for novel devices, as well as extending the
optical spectral range from the visible region to the mid-infrared
region for optoelectronic applications.199
So far, TMDC/bP vertical heterostructures can only be made
by the stacking of components exfoliated using Scotch
tape.200−202 To achieve the scalable production of the
heterostructures, some CVD-based methods have recently
been proposed. For example, Deng et al. reported a high
performance and gate-tunable p−n diode based on n-type
monolayer MoS2/p-type bP. The heterostructures were made by
first putting Scotch-tape-exfoliated bP onto a silicon wafer,
followed by the CVD growth of MoS2 on top of the bP.203 This
approach was also used to fabricate other TMDC/bP
heterostructures, such as MoSe2/bP, etc.204 In addition, recent
work has shown that alloying of bP with arsenic produces b-AsP
with band gaps reaching the long-wavelength infrared regime
(0.15 eV).205 Therefore, fabrication of b-AsP/TMDCs hetero-
structures is another interesting research direction to pursue. As
already mentioned, a transfer method is unavoidable in
fabricating TMDC/bP heterostructures because of the difficulty
of growing bP thin films by CVD. It is obvious that a CVD
approach to grow monolayer or few-layer bP is urgently needed
in order to achieve the all-CVD growth of large area and high
quality TMDC/bP vertical heterostructures. The development
of such a CVD method will significantly accelerate the science
and applications of bP.
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Figure 14. CVD growth of graphene/h-BN lateral 2D heterostructures. (a) Illustration of fabrication procedure for in-plane graphene/h-BN
heterostructures. (b) STEM bright field imaging of graphene/h-BN interface, highlighted by the dashed line. (c) Illustration of epitaxial growth of h-BN
onto graphene edges. Black, blue, red, and small gray spheres represent C, N, B, and H atoms, respectively. (d) Full coverage of etched holes in a
graphene island by BN. (e) Atomic-resolution STM image of graphene/h-BN boundary. A honeycomb lattice and zigzag boundaries are overlaid on the
image. (a, b) Reprinted with permission from ref 219. Copyright 2013, Rights Managed by Nature Publishing Group. (c−e) Reproduced with
permission from ref 179. Copyright 2014 American Association for the Advancement of Science.

5.1.3. Semiconductor/Insulator. It is known that the
surfaces of h-BN are atomically flat, chemically inert, free of
dangling bonds, and surface state free. In addition, the phonon
energy in h-BN is very small, making it a substrate with very weak
electron−phonon interactions. Together, these features make h-
BN an ideal substrate or protective layer for 2D channel materials
to achieve high electronic device performance. For example, an
extremely high Hall mobility of ∼34 000 cm2 V−1 s−1 was
reported for a six-layer MoS2 FET sandwiched between two h-
BN monolayers.206 CVD is seen as a promising way to fabricate
high quality TMDC/h-BN vertical heterostructures. A general
approach is to combine CVD and Scotch-tape exfoliation. For
instance, Yan et al. developed an efficient and scalable CVD
method to directly grow single- and few-layer MoS2 flakes on h-
BN that had been exfoliated using Scotch tape.207 The as-grown
single layer MoS2/h-BN heterostructures have a relatively stable
electrical environment with less electron scattering, and show
potential for use in high quality MoS2-based devices.
Despite the convenience of this combinational method, it is
very difficult to produce large millimeter or centimeter scale
TMDC/h-BN vertical heterostructures. Recently, an interesting
all-CVD method to grow MoS2/h-BN vertical heterostructure
was reported by Wang et al.208 First, a large area h-BN film was
grown on a copper substrate by CVD followed by transfer onto a
SiO2/Si substrate. Second, individual MoS2 domains were grown
directly on the whole h-BN surface with MoO3 and S powders as
precursors. A transfer process was still necessary in this strategy
because the nickel or copper substrate can react with sulfur. To
solve this, a nickel−gallium alloy with an excellent sulfide
resistance and a high catalytic activity for h-BN growth was used
by Fu et al. As exhibited in Figure 13a, this is an all-CVD process
without any transfer steps. Using Mo foil and sulfur powders as
precursors, single crystal, high quality MoS2 domains as large as
200 μm2 were grown on the h-BN surface (Figure 13b,c).
Furthermore, the superior properties (low level of charged
impurities at the interface) of the direct CVD-grown MoS2/h-
BN heterostructure were verified by PL measurements (Figure
13d).176 Another recent study showed that h-BN/MoS2 vertical
heterostructures could be grown on a Au foil using a two-step
CVD method which also did not need a transfer process.34 These
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results indicate that the growth of high quality and large area
TMDC/h-BN heterostructures can be achieved by an all-CVD
approach. Such direct CVD-grown h-BN/MoS2 heterostructures
tend to eliminate contamination introduced in the Scotch-tape-
based transfer approaches, and increase interlayer interactions at
the interface, which may benefit the electronic applications of
TMDCs. Furthermore, these strategies may be used to grow
some metastable 2D materials, where the use of h-BN substrates
may help to stabilize them and further benefit their device
applications.
Except for h-BN, mica has been extensively used as a substrate
for 2D material growth and TMDC/mica vertical hetero-
structures have been reported.209−211 Because of the atomic
flatness, surface inertness, and hexagonal in-plane lattice of mica,
it is suitable for the epitaxial growth of materials with the same
lattice symmetry, such as TMDCs.32 Notably, due to the
flexibility of a mica substrate, this kind of vertical heterostructure
has been used as a flexible and transparent optoelectronic device
with a photoresponse of about 30 mA/W.210
5.1.4. Metal/Insulator. Graphene/h-BN heterostructures
are typical 2D metal/2D insulator vertical heterostructures that
have been extensively studied, because they provide platforms for
novel physics research, including Hofstadter’s butterfly effect, as
well as achieving high-performance graphene electronics.212,213
Generally, Scotch tape exfoliation, CVD growth, and cosegrega-
tion growth are used for the preparation of graphene/h-BN
vertical heterostructures.214,215 The CVD method is the
prevailing one because it has the advantages of growing large
area samples with good thickness uniformity. The commonly
used two-step process for the growth of graphene/h-BN vertical
heterostructures, i.e., growing graphene on top of h-BN layers,216
suffers from the inert catalytic activity of h-BN substrate and a
low decomposition rate of carbon precursors. To solve this issue,
Li et al., have developed an inspiring nickelocene precursor
facilitated route to realize fast growth of graphene/h-BN vertical
heterostructures.217 In this method, h-BN was first grown on a
Cu substrate using ammonia borane as precursors, followed by
graphene deposition through nickelocene decomposition. In this
process, the decomposed carbon rings serve as the carbon source,
while the nickel atoms serve as a gaseous catalyst to increase the
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Figure 15. CVD growth of semiconductor/semiconductor and semiconductor/metal lateral 2D heterostructures. (a) Schematic of synthesis process for
s-MoS2/s-WS2 lateral 2D heterostructures. (b) Atomic-resolution Z-contrast STEM images of in-plane interface betweenWS2 and MoS2 domains. The
orange and pink dashed lines depict the atomic planes along the armchair and zigzag directions, respectively. (c) Combined Raman intensity mapping at
351 (yellow) and 381 cm−1 (purple). (d) Combined PL intensity mapping at 630 (orange) and 680 nm (green). (e) TEM image and corresponding
FFT patterns of WSe2/WO3−x lateral heterostructures, where “H” stands for a hexagonal WSe2 domain and “C” stands for a cubic WO3−x domain. (f)
Schematic of structural evolution during heating of WSe2 in air. (a−d) Reprinted with permission from ref 174. Copyright 2014, Rights Managed by
Nature Publishing Group. (e, f) Reprinted from ref 220. Copyright 2016 American Chemical Society.

growth rate of graphene. The authors have achieved an 8−10
times faster growth rate compared to that without the nickel
catalyst, and large-crystal domains up to 20 μm.
To date, there are few reports on the one-step CVD growth of
graphene/h-BN vertical heterostructures, mainly because it is
difficult to separate the graphene deposition and the h-BN
deposition, resulting in the formation of mixed domains of these
two components. Learning from a recent study that used
reversed flows during the temperature change stage in a
sequential CVD process,218 it is possible to grow graphene/h-
BN vertical heterostructures by a one-step CVD method using a
similar reverse flow method.
5.2. Lateral 2D Heterostructures
Lateral 2D heterostructures refer to heterostructures where each
component is stitched together in the same plane and it is
obvious that there must be strict lattice match requirements for
the components on each side of the interface. Currently,
researchers have grown lateral heterostructures that were metal/
insulator (e.g., graphene/h-BN),179,219 semiconducting/semi-
conducting (e.g., s-TMDC/s-TMDC),177,191 and semiconduct-
ing/metallic (e.g., s-TMDC/m-TMDC).220
5.2.1. Metal/Insulator. Considering their similar lattice
structures and lattice constants (1.7% difference), graphene and
h-BN have the potential to form lateral heterostructures. With
great effort, graphene/h-BN lateral heterostructures have been
realized by different approaches. The first synthesis of this kind of
heterostructure reported was by introducing extra ammonia
borane into the typical graphene growth process.221 The as-
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grown materials are made of randomly distributed domains of h-
BN and graphene. Furthermore, to precisely control the shapes
and sizes of these two components in the heterostructures, the
authors used a two-step CVD method.219 As shown in Figure
14a, h-BN was first grown on copper or nickel foils, and was then
selectively etched away over an exposed region by argon ion
plasma, followed by the growth of graphene at the etched area.
This method is more controllable, and a large area crystal domain
and a highly desired arrangement of heterostructures were
obtained. The high quality nature of the heterostructures was
evidenced by the sharp atomic level boundary (Figure 14b).
Similarly, a two-step CVD approach but with a inverse feed
sequence, i.e., first growing graphene followed by h-BN growth,
was developed by Liu et al. to grow graphene/h-BN
heterostructures.179 In Figure 14c, after the growth of monolayer
graphene, H2 was introduced to in situ etch part of the graphene
to obtain fresh zigzag edges, which immediately act as nucleation
sites for subsequent orientated h-BN growth. As a result, an
atomic level abrupt interface was formed in the graphene/h-BN
lateral heterostructures (Figure 14d,e). It is clear that, after this
great effort, high quality graphene/h-BN lateral heterostructures
with sharp interfaces can now be synthesized by different
methods.
5.2.2. Semiconductor/Semiconductor. Direct CVD
growth has been shown to be very powerful in growing s-
TMDC/s-TMDC lateral heterostructures.218 For example,
MoS2/WS2 lateral heterostructures were prepared by a simple
one-step CVD method with sulfur, molybdenum trioxide, and
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tungsten as precursors (Figure 15a−d).174 An atomically sharp
interface between MoS2 and WS2 was clearly observed with both
atomic planes (armchair and zigzag) sharing the same crystal
orientation. This high quality lateral heterostructure is a
triangular core−shell shape with MoS2 inside and WS2 outside,
as revealed by Raman and PL mapping results. The atomic level
p−n junctions formed between the MoS2 and WS2 deliver a
strong PL enhancement and photovoltaic effect. This one-step
CVD method not only works for the growth of MoSe2/WSe2
lateral heterostructures where the two components have similar
lattice constants, but also works well for 1H MoS2/1T′ MoTe2
lateral heterostructures where the two components have
relatively large lattice mismatch.222,223 In addition, a two-step
CVD method was developed to grow large WSe2/MoSe2
heterostructures, which shows the ability to control both the
shape and size of each TMDC component in the hetero-
structure.195 MoS2/WS2 lateral heterostructures were also grown
by a two-step CVD method using a MoS2 layer as a seed.224
Similarly, lateral heterostructures of MoS2/MoSe2,178 WS2/
WSe2,178 and MoS2/MoS2(1−x)Se2x225 have been synthesized.
These heterostructures have either the same metal elements or
the same chalcogen elements. In a further step, Li et al. use a two-
step epitaxial method to grow WSe2/MoS2 lateral hetero-
structures with good controllability, overcoming the large lattice
mismatch between these two crystals.177 The above results
demonstrate that, among the various s-TMDCs, semiconduct-
ing/semiconducting lateral heterostructures have been success-
fully grown.
5.2.3. Metal/Semiconductor. As mentioned in section 3,
TMDCs can be either metallic or semiconducting, depending on
the phases. For example, 2H phase MoS2 and 2H phase WSe2 are
semiconductors while their 1T phase counterparts are metals.
Taking advantage of this, a general approach to prepare metal/
semiconducting TMDC lateral heterostructures lies in the
treatment of part of an s-TMDC layer to transform it into m-
TMDC. For example, it has been reported that treating CVD-
grown 2H phase WSe2 or MoS2 by n-butyl lithium converted
them both into the 1T phase.226 The FETs made of 2H/1T
lateral heterostructures of WSe2 with metallic phase as contacts
and a semiconductor phase as channel materials exhibit an
excellent FET performance with a mobility up to 66 cm2 V−1 s−1
and on/off current ratios of 107.227 In another interesting study, a
one-step CVD approach was used to grow WSe2−NbSe2 lateral
semiconductor−metal heterostructures with a WxNb1−xSe2
interface region, which can lower the Schottky barrier height of
WSe2 FETs.228 Moreover, even for the same composition, few-
layer 2H/1T′ MoTe2 lateral homostructures were grown by
introducing the proper concentration of Te vapor into
predeposited Mo nanoislands, while a high Te concentration
led to 2H phase and a low one led to the 1T′ phase.229 This lateral
homostructure shows abrupt interfaces with a potential differ-
ence of about 100 eV between the 2H and 1T′ phases.
In addition to the above-mentioned lateral heterostructures
where the 2D components at the interfaces have very similar
lattice constants, there are also several studies on the preparation
of lateral heterostructures which are made of two materials with
very different lattice structures and lattice constants.230−232 For
example, lateral heterostructures made of monolayer MoS2 and
graphene were grown by Zhao et al. The single graphene was first
patterned to form a channel by using an oxygen plasma, and the
graphene edges with dangling bonds promoted MoS2 nucleation
and finally grew graphene/MoS2/graphene heterostructures.230
It is known that monolayer MoS2 has three atomic layers consists
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of S−Mo−S, while monolayer graphene has only one carbon
layer. It will be very interesting to study the interface and binding
between MoS2 and graphene in such heterostructures.233
Recently, electron microscopy was used to study the formation
mechanism of a lateral interface between two components with
large lattice mismatch, such as ZnO/graphene and SiC/
graphene. Moreover, it is revealed that graphene can serve as a
template to grow these novel heterostructures as well as to
stabilize the unstable atomically thin oxides and carbides. These
works significantly extend the range of possible 2D material
based lateral heterostructures.234,235 In addition, we have
developed a simple approach for the preparation of WSe2/
WO3−x in-plane heterostructures by simply heating a CVD-
grown monolayer or few-layer WSe2 in air. As shown in Figure
15e,f, highly conductive WO3−x with a cubic lattice and domain
sizes in the range of a few to a few tens of nanometers were
formed within the hexagonal WSe2 matrix, after heating in air.220
The formation of such WSe2/WO3−x in-plane heterostructures
was found to be able to significantly improve the mobility and
on/off current ratios of WSe2 FETs.
5.3. Other Dimension/2D (xD/2D) Heterostructures
Beyond the 2D/2D heterostructures discussed above, combining
2D materials with other LD materials such as 1D nanowires and
nanotubes, and 0D QDs, atoms, and small molecules (e.g.,
fullerenes, organic molecules) can further expand the family of
2D material based heterostructures. In these, the 2D material is
just like a piece of paper and one can put whatever interesting
materials on top of it in order to achieve certain functionalities.
We term such heterostructures xD/2D heterostructures. It has
been shown recently that putting 0D or 1D materials on top of
2D crystals results in unique electronic and optical properties and
improved device performance in electronics, optoelectronics,
energy conversion, etc.236−238
5.3.1. 1D/2D. One-dimensional materials such as carbon
nanotube and silicon nanowire have tunable morphology, aspect
ratio, doping, and conductivity, as well as the potential to be
aligned into arrays.239 When combined with 2D materials, a large
family of 1D/2D heterostructures and composite materials can
be designed and fabricated, which are interesting for electronic,
optoelectronic, and energy related applications. In addition,
different crystal structures of 1D and 2D materials make the 1D/
2D interface different from 2D/2D ones, and they provide
interesting platforms to study some fundamental science such as
charge transfer at 1D/2D interfaces. Artificial stacking of a 1D
nanowire and a 2D material is a common approach to fabricating
1D/2D heterostructures. There is no strict requirement of lattice
matching for the components, and therefore, numerous
heterostructures have been fabricated.180,240−242 However, the
currently used solution process unavoidably introduces con-
taminants during the preparation. As an improvement,
researchers have developed the growth of 1D nanowires such
as InxGa1−xAs on graphene by MOCVD or molecular beam
epitaxy (MBE) methods.243 In a recent study using a reverse
process, 2D MoS2 nanosheets were grown on 1D MgFe2O4
nanowires to form 1D/2D heterostructures.244
In a recent paper, Li et al. reported a simple one-step CVD
method to grow 1D Bi 2 S 3 nanowires and 2D MoS 2
heterostructures.180 Mixed powders of MoO3 and Bi2O3 were
used as the respective precursors of MoS2 and Bi2S3, and this was
followed by sulfurization at 650 °C. This method produced 1D
Bi2S3 nanowires with a length of 7.3 μm and diameter of 120 nm
on top of 2D monolayer MoS2 flakes (Figure 16a). Although the
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Figure 16. CVD growth of xD/2D vertical heterostructures. (a) Growth and morphologies of Bi2S3/MoS2 heterostructures. (b) Schematic and SEM
image of SWCNT/MoS2/SWCNT vertical point heterostructures. (c) AFM image of the 2D-WS2 crystal after spin coating of CdSe/ZnS 0D-QDs and a
representation of hybrid indirect exciton formation upon photoexcitation. (a) Reprinted from ref 180. Copyright 2016 American Chemical Society. (b)
Reprinted with permission from ref 237. Copyright 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Reprinted from ref 236. Copyright
2016 American Chemical Society.
nanowires were located in random angles with respect to the
lattice of 2D MoS2, it is noted that a relatively high proportion of
nanowires tended to be either parallel or perpendicular to the
edge directions of MoS2, resulting from the low formation energy
barrier in such configurations. Despite this progress, a well-
aligned distribution of Bi2S3 on TMDCs needs to be grown and
studied in-depth in order to fabricate device arrays. In a further
consideration, although m-TMDC nanowire/s-TMDC hetero-
structures have been prepared by steering a focused electronic
beam,245 a simpler way of growing TMDC-based 1D/2D
heterostructures by a CVD method would be promising for
applications and needs to be further explored.
Besides nanowires, carbon nanotubes (CNTs) are another
important 1D material. It is noted that single-wall CNTs
(SWCNTs) can be either semiconducting or metallic, depending
on the way the graphene sheet is wrapped in the tube, especially
the chirality.246 SWCNTs will different chiralities have different
band gaps and band positions, which in combination with many
different TMDCs would result in a multitude of combinations of
energy alignments at the interface between a 1D SWCNT and
2D TMDCs. Considering the facts that researchers have made
significant progress in the chirality-controlled synthesis of
SWCNTs and can now produce high purity single chirality
SWCNT species,246,247 it is reasonable to anticipate that 1D
SWCNT/2D TMDC heterostructures have much science to be
explored and may show promising applications.
For example, recently, by using an SWCNT as a p-type
semiconductor and monolayer MoS2 as an n-type semi-
conductor, gate-tunable mixed p−n heterostructures were
formed.248 In a further step, Zhang et al. reported the
construction of SWCNT/MoS2/SWCNT vertical heterostruc-
tures, where the MoS2 monolayer was sandwiched between two
cross-stacked metallic SWCNTs and the contact areas were as
low as 1−2 nm. The device was stacked in the following
sequence. Scotch-tape-exfoliated MoS2 layer was first transferred
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onto CVD-grown horizontally aligned SWCNTs, followed by
the transfer of another SWCNT layer aligned perpendicular to
the first layer, on top of MoS2. A schematic and SEM image of the
device are shown in Figure 16b. The fabricated FET exhibits a
high on/off current ratio of 105−106 at room temperature, and
shows its superiority in making nanoscale 2D material based
devices for logic circuits.237 Notably, FETs with ultrashort gate
electrodes have been fabricated using this 1D/2D hetero-
structure design.238 These noble-metal-free electrode devices are
promising for scalable applications in nanodevices.249
As a complement to the 1D nanowire/2D TMDCs and 1D
SWCNT/2D TMDC heterostructures, 1D TMDC nanoribbon/
2D TMDCs demonstrate great potential in unique applications
that differ from the 2D TMDC/2D TMDC heterostructures,
because of the metallicity at inversion domain boundaries in the
1D structure.250 However, this novel structure has seldom been
reported. Further attention should be paid to novel properties
and applications, and more effort needs to be devoted to the
CVD growth of 1D TMDC nanoribbon/2D TMDC layered
heterostructures.
5.3.2. 0D/2D. QDs are typical 0D materials, which have a
large variety, a broad size tunability, and a tunability of band gaps.
When QDs are in contact with 2D materials, the interface may
exhibit interesting properties such as nonradiative energy
transfer, charge transfer, and surface plasmonic effects, making
such 0D/2D heterostructures increasingly attractive for catalysis
and optoelectronic applications.251
In general, the QDs are prepared by solution-based methods,
followed by dispersion on the surface of 2D materials. Using this
strategy, Boulesbaa et al. reported 2D WS2 monolayer/CdSe−
ZnS core−shell QD heterostructures, which show ultrafast
charge transfer, where the WS2 monolayer was grown using CVD
and the CdSe−ZnS QDs were spin-coated onto the WS2. In
Figure 16c, the height of the WS2 is 0.7 nm and the height of the
CdSe−ZnS QDs is about 8 nm with a uniform coverage on the
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Figure 17. Electronic devices for 2D materials and heterostructures. (a) Schematic of 1D/2D-FET with MoS2 channel and SWCNT gate. (b) False-
colored SEM image of the device. (c) Cross-sectional TEM image of representative sample showing SWCNT gate, ZrO2 gate dielectric, and bilayer
MoS2 channel. (d) ID−VGS characteristics of bilayer MoS2 channel SWCNT gated FET at VBS = 5 V and VDS = 50 mV and 1 V (left) and ID−VGS
characteristics at VDS = 1 V and varying VBS (right). (e) Schematic showing cross-sectional view of an ATLAS-TFET with ultrathin bilayer MoS2 as the
channel and p-type Ge as the source. (f) Cross-sectional TEM image of bilayer MoS2 on Ge. Scale bar, 2 nm. (g) Drain current as a function of gate
voltage for drain voltages of 0.1, 0.5, and 1 V. (h) SS as a function of drain current for an ATLAS-TFET (green triangles) as well as a conventional
MOSFET (blue squares) at VDS = 0.5 V. (a−d) Reproduced with permission from ref 238. Copyright 2016 American Association for the Advancement
of Science. (e−h) Reprinted with permission from ref 275. Copyright 2015, Rights Managed by Nature Publishing Group.

WS2 surface. These heterostructures form indirect excitons by
hole and electron transfer through the interface under the
illumination of laser light.236 Similarly, PbS colloidal QD/2D
WSe2 heterostructures have been developed and used as high
sensitivity and broadband photodetectors.252 QD/TMDC
heterostructures of CdS/MoS2 were also formed to produce a
high performance photocatalyst for the hydrogen evolution
reaction,253 and this potential heterostructure need also be
grown by CVD in the future. To achieve more accurate
deposition by additives, a CVD method combined with thermal
evaporation was used to synthesize PbS/MoS2 heterostructures,
where the edges of nonlayered PbS nanoplates were in contact
with the edges of MoS2.254 Very recently, C60 molecules were
deposited onto graphene using a low temperature effusion cell at
156 °C,255 and the heterostructures showed good electronic
properties in terms of an on/off current ratio above 3 × 103.256
Based on these results, we believe this approach can be an
effective way to obtain C60/TMDC heterostructures for new
types of electronic devices.
6. APPLICATIONS OF CVD-GROWN 2D MATERIALS
AND THEIR HETEROSTRUCTURES
The rapid developments in the CVD technique have shown the
ability to grow large-area high quality 2D materials with versatile
structures and properties, and the growth of 2D material based
vertical and lateral heterostructures. The availability of such
material systems provides a foundation for the exploration of
their uses in various fields. In this section, the uses of CVD-grown
2D materials and 2D heterostructures for electronics (section
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6.1), optoelectronics (section 6.2), sensors (section 6.3), flexible
devices (section 6.4), and catalysis (section 6.5) are discussed.
6.1. Electronics
The FET is the most fundamental and important component in
electronics. In a typical FET device, a channel material is
connected to contact pads called source and drain electrodes on
both sides, as well as to a top gate electrode with a dielectric layer
between the channel material and the gate electrode. The current
flow in the channel is associated with the source−drain voltage
(VDS) and can be modulated by the electric field through the
applied gate voltage (VG). For high performance FETs, (i) the
charge carrier mobility and on-state current (Ion) should be high
enough to realize a fast response, and (ii) the on/off current ratio
of the FET should be large and the leakage current at the off state
(Ioff) should be as low as possible, in order to achieve effective
switching and low power consumption during transistor
operation.
The well-known Moore’s law predicts that the numbers of
transistors per unit area will double every 18 months, indicating
that each transistor will become smaller and smaller. One
obvious problem for small transistors is the so-called short
channel effect; i.e., the effect of source−drain voltage on the
channel material would impair the ability of gate voltage to tune
the channel current flow, resulting in a bad switching
performance. Another problem is the heat dissipation, where
the accumulated heat may seriously degrade device performance,
cause technical failure, and reduce the lifetime. In addition, future
devices require electronics to be not only small in size and fast in
operation speed, but also to have multiple functionalities such as
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being flexible, wearable, power efficient, or even self-powered.
Taken together, these exacting requirements stand as significant
challenges for current silicon and III−V semiconductors, and
provide exciting opportunities for new semiconducting materials,
especially LD materials such as 2D graphene, TMDCs, bP, etc.
Taking 2D TMDCs as an example, they are atomically flat with
excellent mechanical flexibility, and free from dangling bonds and
surface states. In addition, the availability of a large number of
TMDCs with diverse electronic properties and different band
gaps have made them being used to fabricated TMDC-based
FETs with a high on/off current ratio and a low off current,257 as
well as high mobility.258 In the following paragraphs, we highlight
the latest strategies to optimize the FET performance of 2D
transistors, mainly based on the improvement of CVD-grown
TMDCs.
High mobility is very important for many electronic
applications including FETs and radio frequency devices.
Recently, charge scattering mechanisms259,260 in TMDCs have
been extensively studied to achieve a high charge carrier mobility
in FETs. For example, the first monolayer MoS2-based FET with
high a mobility of 200 cm2 V−1 s−1 and a high on/off current ratio
of 108 at room temperature was reported in 2011,261 where the
researchers used Scotch-tape-exfoliated MoS2. CVD-grown
TMDCs with high quality and large area have recently been
used to fabricate MoS2, MoSe2, WS2, and WSe2 FETs with
superior performance.27,262 Notably, Yu et al. used a “gate first”
process to fabricate FETs with a high mobility using CVD-grown
MoS2 as the channel material, and then to fabricate various logic
gates and circuits for large area high performance electronics.263
In addition to the above typical TMDC materials, newly
emerging 2D materials, such as PtSe2, have been grown by
CVT and exhibit a high room temperature mobility of 210 cm2
V−1 s−1 and good stability in a back gate FET.264 To date, high
mobility individual 2D-material-based FETs have been realized
using an ionic liquid as the gate dielectric, decreasing the number
of charge traps, or making good electrode/channel material
contacts, etc.142,265−268
Another important research direction is to decrease the device
size of 2D material based FETs. To achieve this goal, a MoS2-
based FET with a narrow SWCNT (diameter ∼ 1 nm) as gate
electrode has been designed and fabricated by Desai et al. (Figure
17a−c).238 In this structure, the aligned SWCNTs were grown by
CVD, followed by ALD deposition of a ZrO2 gate dielectric.
Later, Scotch-tape-exfoliated MoS2 channel material was put on
top of the ZrO2. The ID−VGS characteristics in Figure 17d at VBS
= 5 V and VDS = 50 mV and 1 V demonstrate the ability of the ∼1
nm SWCNT gate to deplete the MoS2 channel and turn off the
device. The FET exhibited excellent subthreshold characteristics
with a subthreshold swing (SS) of ∼65 mV/decade (dec) and a
high on/off current ratio of ∼106. Moreover, with the increase of
the VBS values, VGS had to decrease in order to deplete the MoS2
channel, which in turn made the threshold voltage (Vth) more
negative. Above VBS = 1 V, the SS and ION did not improve any
further, and the extension regions were strongly inverted. Thus,
the 1D/2D FET operated as a short-channel device. In achieving
an ultrashort channel length, Xu et al. reported a more universal
technological technique to make sub-10-nm gaps with sharp
edges and steep sidewalls, exhibiting no obvious short channel
effects.269 This monolayer MoS2 FET shows a high on/off
current ratio of 106 and an SS of 140 mV/dec. With a decrease of
both the gate length and the channel length, the heat dissipation
from electronics has emerged as a crucial problem that deserves
more attention.
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The emergence of 2D/2D heterostructures has produced a
platform for the design of novel structure and high performance
FETs. With stacked 2D materials as a conductive channel,
decreased gate voltage and power consumption can be realized
for electronics. Previously, MoS2/WSe2,270,271 WSe2/SnSe2,272
bp/MoS2,273 and MoS2/α-MoTe2274 based vertical hetero-
structures have been used for tunneling FETs using the
Scotch-tape-exfoliation method. In a further step based on the
CVD growth of MoS2, Sarkar et al. reported the fabrication of an
atomically thin and layered semiconducting-channel tunnel FET
device as shown in Figure 17e,f.275 In this structure, the substrate
consisted of a p-doped Ge wafer with parts of it being a 300 nm
SiO2 dielectric layer, bilayer MoS2 synthesized by CVD was then
transferred onto this engineered substrate, and the Ge contacts
the source electrode while MoS2 contacts the drain electrode
making a unique tunneling structure. A solid polymer electrolyte
composed of poly(ethylene oxide) and lithium perchlorate was
used as a high quality gate dielectric material. For this band-to-
band tunneling device, the transfer characteristics (Figure 17g)
for different VDS’s shows that the atomically thin and layered
semiconducting-channel tunnel FET (ATLAS-TFET) can
overcome the fundamental limitations on SS (60 mV/dec at
room temperature) in conventional MOSFETs, and SS values
below 60 mV/dec were obtained over about 4 decades of current.
As shown in Figure 17h, the lowest SS for the ATLAS-TFET can
be as low as 3.9 mV/dec, and excellent average SS values of 5.5,
12.8, 22, and 31.1 mV/dec were obtained over 1, 2, 3, and 4
decades of current, respectively. The design of these tunneling
FETs largely increases the gate capability to control the channel
mobility. To facilitate the fabrication process without using a bulk
p-type three-dimensional Ge substrate, the 2D/2D hetero-
structures such as MoS2/WSe2 need to be grown by CVD for the
production of tunneling FETs.
6.2. Optoelectronics
An optoelectronic device features a mutual charge-to-photon
conversion process. For a light-emitting device, photons are
generated due to the recombination of electron−hole pairs,
which are injected from a cathode and an anode, respectively.
The light emission process is named “electroluminescence”
(EL). For a photovoltaic device, free charges are generated due to
the dissociation of excitons, which are excited by the incident
photons. Two typical applications of photovoltaic cells include
solar cells and photodetectors. Generally, a semiconductor with a
direct band gap has high efficiency of exciton formation or
recombination. As a result, an optoelectronic device with an
active semiconductor of a direct band gap shows higher device
efficiency in comparison with that of an indirect band gap. For
2D materials, most direct band gap semiconductors are TMDC
monolayers. Consequently, 2D optoelectronic devices select
TMDC monolayer as the active layer. It is important to note that
several TMDC multilayers can also have a direct band gap due to
the introduction of tensile strain.276 Based on the above
considerations, TMDC-based LEDs, photodiodes, and solar
cells will be briefly introduced in sections 6.2.1, 6.2.2, and 6.2.3.
6.2.1. LEDs. An LED structure typically has a p−n junction.
Under a given bias, electrons and holes can be injected from
electrodes into n-type and p-type semiconductors, respectively.
In the depletion area of a p−n junction, the electrons and holes
form excitons or electron−hole pairs, which undergo recombi-
nation and emit photons. The EL spectra for an LED can cover
the ultraviolet, visible, or infrared range by selecting active
semiconductors of proper band gaps. Commonly, a high-
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Figure 18. Optoelectronic devices based on 2D materials and heterostructures. (a) Schematic view and I−V characteristic of p+-Si/i-WS2/n−-ITO
heterostructured device. Inset shows images of LEDs and EL mapping. Current-dependent (b) EL spectra and (c) degree of EL circular polarization for
full emission and each component emission of the LED device. (d) Schematic view of electron−hole pair generation under laser beam illumination and
hole tunneling across the h-BN layer. (e) I−V characteristic of the photodetector under the dark and excitation of 405 nm laser light. (f) J−V
characteristics, EQE spectra, and parameters of MoS2/p-Si heterostructured solar cells. (a−c) Reprinted from ref 303. Copyright 2014 American
Chemical Society. (d, e) Reprinted from ref 287. Copyright 2016 American Chemical Society. (f) Reprinted from ref 297. Copyright 2016 American
Chemical Society.

performance LED shows high internal quantum efficiency (IQE)
and high external quantum efficiency (EQE). IQE is the ratio
between the numbers of emitted photons from the active layer
and injected charge from electrodes, while EQE represents the
ratio between the numbers of photons escaping from the device
and injected charges from electrodes. For 2D LEDs, the structure
of the active layer has evolved from a single layer277,278 to
heterostructures.279,280 Meanwhile, the emitted light can be
modulated to have circular polarization,281,282 consist of a single
photon,283,284 etc.
Recently, by employing TMDC materials as active layers, high-
performance 2D LEDs have been fabricated, which are grown by
CVD method. For example, a 2D vertical heterostructure of p-
type MoS2/n-type MoS2 has been attained by using a two-step
CVD method. A white-light LED based on the heterostructure
exhibits an extremely high efficiency.285 Other heterostructures,
such as WSe2/MoS2 and MoSe2/WSe2, have also been developed
and are promising for applications in the fields of display and
lighting.286 In addition to the p−n heterostructure, Yang et al.
reported a p−i−n heterostructure, in which the optical chirality
can be electrically tunable. Meanwhile, the simple fabrication
method enables the massive production of 2D LEDs.287 Figure
18a shows a 2D LED with an emissive layer, namely, CVD-grown
WS2monolayer, sandwiched between a heavily p-doped Si anode
and an n-ITO cathode. The I−V characteristic shows a typical
rectifying behavior. Turn-on voltage is as low as 2 V. A dual-peak
EL spectrum is measured at the low temperature of 77 K. Figure
18b shows that, at different driving currents, the X− peak
intensity increases more rapidly than that of Xb, resulting in the
electric-field-modulated color of the CVD-grown LED.
Furthermore, circularly polarized EL can be achieved from the
CVD-grown WS2 as demonstrated in Figure 18c. The right-
handed circularly polarized light is stronger than the left-handed
one at all driving currents. Either the total or each component of
X−, Xb, and X0 decreases with the current, indicating the electric-
field-modulated circular polarization degree. Based on these
results, it can be further proposed that TMDC monolayer can be
possibly employed as the buffer layer to facilitate the charge
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injection from electrodes to the emissive layer. Another
important function of 2D LEDs is the single-photon emission,
which has been observed at edges of WSe2 crystals at low
temperature, featuring a 0.1 meV line width.283,288,289 In this
case, it can be anticipated that the higher single-photon-emission
efficiency can be achieved by precise control over edge structures
and defects during the CVD growth process, and thus promote
the development of future applications.
6.2.2. Photodetectors. For a photodetector, a built-in
electric field is formed, and crosses the depletion region of the p−
n junction. The electron−hole pairs, excited by the incident light,
are dissociated into free electrons and holes by the built-in field.
Under driving of the applied bias, the free charges transport
across the active layer, followed by the collection of electrodes,
which finally contribute to the photocurrent. In addition, the
sensitivity to the wavelength of the incident light is crucial for the
device selectivity. To achieve high performance, a thick depletion
region is preferred to harvest more incident light for the
generation of more electron−hole pairs, while p-type and n-type
layers on two sides of the junction are kept thin enough to
shorten the charge transport distance, ensuring the high
responsivity.290 Several significant progresses, including the use
of individual TMDC layers,291,292 2D/2D heterostructures,293
1D/2D heterostructures, and novel 0D/2D heterostructures,294
have been made to optimize both absorption and transport
distance.
Among different types of heterostructures, TMDC ones are
promising for advanced photodetectors. Especially for type II
band alignment, the dissociation efficiency of electron−hole
pairs is very high due to the existence of a strong built-in electric
field.295,296 As an example, the typical time constant of hole
transfer has been observed to be <50 fs in MoS2/WS2 vertical
heterostructures.189 Some other TMDC heterostructures show
great promising applications as active layers of high-performance
photodetectors, such as few layers of MoS2/WS2,196 and MoS2/
h-BN/graphene. The photodetectors based on the TMDC
heterostructures demonstrate high performance, including the
high photocurrent/dark-current ratio, high photoresponsivity,
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and high photodetectivity devices.297 Figure 18d shows an
asymmetric tunneling structure, which has been both theoret-
ically and experimentally demonstrated to facilitate the
dissociation of the electron−hole pairs. Holes can tunnel across
the h-BN and reach the graphene layer while electrons are
reserved in the MoS2 layer. Experimental results show that a 7 nm
h-BN layer has the optimized thickness for the best performance
device under a certain illumination. As depicted in Figure 18e, the
photocurrent exhibits linear dependence on the drain bias,
suggesting the Fowler−Nordheim tunneling mechanism. The
dark current shows logarithmic and linear dependence on the
drain bias at low and high ranges, respectively. Therefore, a high-
performance photodetector can be obtained by employing 2D h-
BN with the proper thickness as the tunneling layer. Recently,
0D-QDs/2D-TMDCs have been fabricated for the photo-
detector applications, because of their ultrafast charge transfer
process between QD and TMDC. It is important to note that the
size-dependent band structure of QDs enables the tunable light
detection of QD/TMDC based photodetectors.
6.2.3. Solar Cells. The working principle of a solar cell is
similar to that of a photodetector. Differently, the solar cell works
as the electric power source; hence, no external bias is required.
In addition, unlike the requirement of selectivity for a
photodetector, absorption in the wide wavelength range is
highly preferred for solar cells, so as to maximize solar energy
harvesting. Desired solar cells typically have high open-circuit
voltage (Voc), high short-circuit current (Jsc), and high fill factor
(FF). Photons with energy of 1−3 eV dominate the solar light.
TMDC materials have broad band gaps in the range 1−3 eV,
which is consistent with those of solar photons. Therefore,
designing the proper heterostructures, which can effectively
combine TMDC materials with different band gaps, will offer a
promising solution of the full spectrum absorption of solar
light.298 Based on the strategy, TMDCs and their hetero-
structures have been developed and employed as active layers of
solar cells, which are characterized to have a high fill factor and
broad band absorption.299−302
Tsai et al. reported the CVD fabrication of large-scale n-type
MoS2 monolayer/p-type Si heterostructure.303 Figure 18f shows
the J−V curve of the MoS2/p-Si based solar cell. Voc, FF, and Jsc
are calculated to be 0.41 V, 57.26%, and 22.36 mA/cm2,
respectively. The power conversion efficiency reaches 5.23%,
which is dominated by the large built-in field crossing the MoS2/
p-Si interface. The high Jsc in conjunction with the high EQE is
ascribed to the broadband absorption and efficient electron−
hole pair dissociation. In addition to the single TMDC materials,
TMDC/TMDC heterostructures, such as MoS2/WSe2, MoSe2/
WSe2, and MoS2/graphene/WSe2, show great potential in high-
efficiency photovoltaic cell applications.298,304−306 Note that
these heterostructures are fabricated by using exfoliated
materials, which have a relatively small scale. Therefore, it is
highly required to fabricate large-scale heterostructures in the
future for their practical applications. Among all methods, CVD
is the ideal candidate to achieve the goal. Former first-principle
calculations have revealed that the C60(0D)/WS2(2D) hetero-
structures can function as efficient active layers for excitonic solar
cells.307 However, there is limited report on the use of 0D/2D
heterostructures in solar cells. This provides great opportunities
for researchers to make efforts in the realization of more 0D/2D
heterostructures by CVD methods.
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6.3. Sensors
The exposure of a large number of surface atoms in 2D materials
makes them very sensitive to the external environment, such as
temperature, mechanical stress, chemical substances, magnetism,
etc. In addition, the tunable band gap, liquid medium stability,
and low toxicity of 2D materials make them especially suitable for
various sensors.308 For 2D semiconductor-based sensors, the
input and output signals are generally electric signals, which can
be modulated as a function of the external conditions by charge
transfer processes. In recent years, researchers have developed
the use of advanced 2D material based sensors for use as
humidity sensors,309 gas sensors,310−312 soluble ion sensors,313
biosensors,314,315 strain sensors,316 etc.
Molecule sensors are very widely used in our daily lives. Gas
sensing, especially toxic gas detection, is necessary in chemical
and safety fields. It has been demonstrated that a graphene-based
micrometer-size sensor is capable of detecting individual
molecules on its surface.317 For TMDCs, Liu et al. reported
the use of a CVD-grown monolayer of MoS2 for room
temperature trace chemical detection by using Schottky
contacted FETs.318 These back gate transistors show 2−3 orders
of magnitude current changes when exposed to low concen-
trations of NO2 and NH3. As shown in Figure 19a,b, the MoS2
Figure 19. Sensors made of 2D materials and their heterostructures. (a)
Conductance change of MoS2 FETs upon exposure to 400 ppb NO2. (b)
Conductance change of MoS2 FETs upon exposure to 500 ppm NH3.
(c) Change in relative resistances and gauge factors as a function of
applied tensile and compressive strain in a linear region (from −1.98 to
1.98%). (d) Tracking results for the position of a moving, touching pen
(diameter = 2 mm) on a tactile sensor. (a, b) Reprinted from ref 318.
Copyright 2014 American Chemical Society. (c, d) Reprinted with
permission from ref 316. Copyright 2016 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim.
sensors show a current decrease by a factor of 174 under 400 ppb
NO2 and a current increase of 1218 under 500 ppm NH3. These
results can be attributed to Schottky barrier modulation at the
interface of the metal electrode and MoS2 channels, in addition to
charge transfer between the absorbed gas and the MoS2 layers. In
another respect, 2D material based biomolecule detection is an
important direction in biomedical engineering and disease
diagnosis.319 Naylor et al. reported the fabrication of large arrays
of back gate FET biosensors using CVD-grown MoS2.320 An
atomic length nickel mediated linker makes the biomolecules
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Figure 20. Flexible and transparent devices made of 2D materials and their heterostructures. (a) Structure of a FET on a flexible PET substrate and its
transfer characteristics. (b) Optical image of an as-fabricated FET. (c) Device characteristics of flexible FETs under strain. (d) Schematic of a monolayer
graphene/MoS2 flexible photodetector which is side-gated with a PE. (e) Picture of a typical photodetector, showing transparency and flexibility. (inset)
Optical image of four photodetectors. (f) Schematic three-point bending setup. LD = laser diode; FC= fiber collimator. (inset, left) Iph,bend normalized to
the value at rest Iph,rest as a function of rb, (inset, right) and Iph,bend normalized to the value at rest Iph,rest as a function of the number of bending cycles. (a−
c) Reprinted from ref 324. Copyright 2014 American Chemical Society. (d−f) Reprinted from ref 326. Copyright 2016 American Chemical Society.

come closer to the MoS2 surface thus maximizing the sensitivity,
and as a result, the device shows a high detectivity.
A tactile sensor is a key component in realizing wearable
applications such as electronic skin and health care monitoring
systems. Recently, Park et al. synthesized wafer-scale bilayer
MoS2 continuous films by CVD and used them as channel
materials for the fabrication of MoS2-based tactile sensor arrays
with a size of 2.2 cm × 2.2 cm.316 For these arrays, graphene was
used as the conductive electrode and MoS2 as active channel
materials. The compressive and tensile tests of the MoS2 strain
sensors in a linear strain region of −1.98 to 1.98% showed that
the resistance change and the strain are linear, showing very good
sensitivity (Figure 19c). Furthermore, a quick change in strain on
the tactile sensor can be easily detected (Figure 19d), proving its
practical value for electronic skin applications. Alternatively,
large-area, few-layer MoS2 films were grown by sulfurization of
predeposited molybdenum films and have been further used in
miniature fiber-optic Fabry−Perot pressure sensors with a high
deflection sensitivity of 89.3 nm Pa−1 at low acoustic
pressures.156 Considering the applications of 2D material based
sensors, more effort needs to be devoted to the preparation of
large-area 2D materials for sensor arrays as well as the
improvement of their stability, response, and selectivity for
future applications.
6.4. Flexible and Wearable Devices
The ultrathin body and good mechanical properties of 2D
TMDC materials make them attractive for use in flexible and
transparent electronic and optoelectronic devices.321,322 The
recent progress in growing large area TMDC layers on flexible
substrates was reviewed in section 4.3. In this section, we will
focus on the applications of 2D materials for flexible and
transparent devices, which will be important in the future.
For the fabrication of flexible electronic devices, each
component should be flexible.323 To realize this goal, Das et al.
reported the fabrication of all 2D material based transistors,
where they used Scotch-tape-exfoliated WSe2 as channels, CVD-
grown graphene as contact electrodes, CVD-grown few-layer h-
6119
BN as dielectric, and PET as the flexible substrate on which the
devices were made.324 As shown in Figure 20a−c, the transfer
and output characteristics of the flexible devices demonstrated
low contact resistance and a high on/off ratio, and this
performance can be maintained under an in-plane mechanical
strain up to 2%. In a further step, large area continuous MoS2
films were used as channels for top gate flexible FETs on a PET/
PDMS substrate, which showed high performance with a
mobility of about 14 cm2 V−1 s−1 and an on/off current ratio
of 105.325 For flexible optoelectronic devices, De Fazio et al.
reported a large area, flexible graphene/MoS2 vertical hetero-
structure based photodetector on a PET substrate, where
centimeter-scale monolayer graphene and MoS2 were grown
by CVD (Figure 20d).326 The photodetector in Figure 20e has
transparency and flexibility and shows a large photoactive area,
high photoresponse, and high transparency. In terms of
flexibility, the photodetectors show that the normalized
photocurrent deviations were within 15% at a small bending
radius of 1.4 cm, and the performance was well retained after
several bending cycles (Figure 20f). Recently, strain-induced
band gap tunability in TMDCs has attracted great atten-
tion.327,328 Flexible electronics and optoelectronics that can be
stretched, compressed, and bent have provided a valuable
platform for engineering the properties of 2D materials by
applying strains.
6.5. Hydrogen Evolution Reactions
As a class of promising alternative materials to platinum for
hydrogen generation through the electrolysis of water, 2D
materials, especially TMDCs, show great importance in the
hydrogen evolution reaction (HER).329,330 For example, MoS2
shows great potential for HER in the following three aspects: (i)
The hydrogen adsorption free energy ΔGH of MoS2 edges is
around 0.1 eV, very close to that of the platinum, which could
facilitate both H* adsorption and H2 desorption. (ii) The
exchange current density of MoS2 edge sites is also comparable to
those of the noble metals, corresponding to a higher electron
transfer rate and kinetic activity of the HER. (iii) The metallic
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Figure 21. HER for 2D-based materials and heterostructures. (a) Free energy versus reaction coordinates of HER for S-vacancy range of 0−25% in
MoS2. (b) AC-TEM image of MoS2 monolayer with about 11.3% S vacancies. (c) Schematic showing monolayer MoS2 on gold foil for HER. (d)
Coverage-dependent polarization curves of as-grown monolayer MoS2 on Au foil. (e) Schematic of the three electrodes for HER catalytic measurements
with field effect modulation. (f) Polarization curves of HER at different back gate voltages. (a, b) Reprinted with permission from ref 340. Copyright
2015, Rights Managed by Nature Publishing Group. (c, d) Reprinted from ref 344. Copyright 2014 American Chemical Society. (e, f) Reprinted with
permission from ref 336. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

phase of MoS2 (1T MoS2) with high conductivity could further
increase the HER performance.
Taking advantage of these facts, 2D material based HER
research has gained great attention. From our point of view, the
intrinsic reason for the improvement of HER performance must
be ascribed to the narrow band gap of the materials. Theoretical
calculations have predicted some key points in optimizing the
HER performance of monolayer TMDCs.331,332 Up to now,
many strategies have been used to optimize the HER catalytic
activity including creating more active sites,333−335 increasing the
conductivity through control of the field effect,336 heteroatom
doping,337 etc.
Due to the limited number of edge sites in certain 2D
materials, creating extra edge sites is a straightforward approach
to improving catalytic activity. Li et al. grew small MoS2
nanosheets perpendicular to the substrate, increasing the number
of edge sites in this area. Such kinds of high-porosity network
structures are formed by using a vertically configured substrate in
a typical CVD system.338 Apart from making edge sites,
introducing active sites by creating sulfur vacancies to activate
the in-plane surface is also a powerful method.339 Zheng et al.
used CVD to grow MoS2 that was enriched with sulfur vacancies
by Ar plasma treatment.340 The free energy of hydrogen proton
absorption on a MoS2 surface decreases with an increase in the
number of in-plane sulfur vacancies (Figure 21a,b). The
appropriate zero-around ΔGH of the in-plane surface provides
more active sites for H* adsorption and H2 desorption, resulting
in an enhanced HER activity with an overpotential of around 250
mV for a current density of 10 mA cm−2, and a Tafel slope of
about 82 mV dec−1. In a further step, a remote hydrogen plasma
provided a more controllable way to generate S vacancies and to
activate the basal plane.341 To deeply understand the HER
kinetics of the above-mentioned S vacancies, Li et al. used
scanning electrochemical microscopy to systematically study the
kinetic behavior, showing that a 4 times enhanced electron-
transfer rate with sulfur vacancies is responsible for the improved
HER activity.342
To increase the electronic conductivity, one commonly used
method is to convert the 2D material from a semiconductor
phase to a metallic phase. Yuan et al. reported the CVD growth of
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hexagonal 1T phase VS2 single crystals, which show a low
overpotential of 68 mV at 10 mA cm−2 and a small Tafel slope of
34 mV/dec for electrocatalytic HER activity.343 Another very
useful approach is to combine the 2D materials with conductors
such as graphene, carbon nanotubes, and metal foil. Shi et al. first
reported the growth of monolayer MoS2 on highly conductive Au
foils by a low pressure CVD method.344 Because of the strong
electron coupling between MoS2 and the conductive substrate,
the device exhibited improved catalytic performance as shown in
Figure 21c,d.
Very recently, to reduce the contact resistance between
electrode and catalyst and facilitate electron injection into active
sites, Wang et al. reported a field effect modulated single MoS2
HER device.336 The catalytic activity was boosted by an increase
of the back voltage, and by applying a back voltage at 5 V, the
overpotential (exchange current density of 100 μm cm−2) was as
low as 38 mV with a lower Tafel slope (Figure 21e,f). This is the
result of the movement of the Fermi level of the n-type MoS2
closer to the bottom of the conduction band by the positive
electric field resulting in fast electron transfer. Similarly, this field
effect tuning method may be used in some kinds of CVD-grown
high quality 2D heterostructures for HER.
In addition to the use of individual 2D materials for HER, 2D
material based heterostructures have shown advantages in terms
of fast charge transfer, flourish surface electron state, and
decreasing contact resistance, which may lead to improved HER
performance.329,345 For example, Tang et al. reported the design
and growth of 3D mesoporous graphene/nitrogen-doped MoS2
vertical heterostructures through a two-step CVD method.346
The modification in morphology, interface, and edge site have
resulted in an accelerated rate for hydrogen evolution. By
changing the individual TMDC into alloy, the WxMo1−xS2/
graphene heterostructures exhibit an onset potential of 96 mV
and a Tafel slope of 38.7 mV/dec in HER.347
By the modifications of 2D materials mentioned above, a lower
onset potential, higher current density, and smaller Tafel slope of
the HER properties are observed. Despite all these improve-
ments, in order to use TMDC materials in practical hydrogen
generation, some effort needs to be paid to increasing the range
of electrolytes (such as alkaline solution and seawater) beyond
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Chemical Reviews
Figure 22. Proposed road map to further push the science and technology of CVD-grown 2D materials in the next five years.
acid solutions. In a more environmentally friendly way,
photoelectrochemical hydrogen generation would be more
effective. Because energy and charge transfer between TMDCs
and QDs can be increased,236,251 their photoelectrochemical
catalytic activity will be greatly improved.
7. CONCLUDING REMARKS AND OUTLOOK
In this review, we have highlighted recent achievements in the
CVD growth of 2D materials, focusing on TMDCs and their
heterostructures and the applications of these materials in
electronics, optoelectronics, sensors, flexible devices, and
catalysis. Regarding the growth of single crystal TMDCs, based
on an understanding of the nucleation and growth mechanism,
we have reviewed key CVD growth strategies developed for
controlling the crystal size, number of layers, crystal orientation,
morphology, phase, and doping of 2D TMDCs. Defect
formation and their recovery mechanisms in 2D materials have
also been discussed, since a deep understanding of defects would
help in improving the quality of 2D materials. We have further
summarized the state-of-the-art methods developed to grow
wafer-scale homogeneous and continuous 2D films on rigid as
well as flexible substrates. We then discussed current strategies to
grow 2D material based heterostructures including vertical,
lateral, and xD/2D heterostructures. Lastly, we demonstrated
several applications of CVD-grown 2D materials and their
heterostructures.
In the past several years, CVD methods have been extensively
developed to grow 2D materials, and high quality 2D crystals,
continuous films, and even heterostructures have been grown
with a large-scale production capability and good controllability,
which are of great important for bringing practical applications to
fruition. In addition, there has been great success in using these
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CVD-grown 2D materials in new high-performance, advanced
concept devices. However, the CVD growth of 2D materials is at
an early stage and many challenges remain. For example, (i) more
effort must be devoted to obtaining a deep understanding of the
fundamental mechanisms of CVD growth methods in order to
improve the reproducibility of the growth of 2D materials, (ii)
new approaches must be developed to facilitate the growth of
wafer-scale 2D single crystals and continuous 2D films for
practical uses, and (iii) 2D heterostructures need to be extended
to many other substances as well as new types of structures and
junctions, etc. In sections 7.1−7.8 we envision eight directions to
which we should pay particular attention to further advance the
science and technology of CVD-grown 2D materials (Figure 22).
7.1. Improvement and Innovation of CVD Growth Systems
As discussed above, the growth of TMDCs usually involves solid
precursors, whose concentrations are difficult to control
precisely. This point is very different from that in the typical
CVD growth of graphene, where stable concentrations and
constant feeding of CH4 and H2 are easy to maintain over a long
growth period, leading to the growth of graphene with good
controllability. To learn from graphene growth, several efficient
methods, such as MOCVD, have been developed aimed at
obtaining stable precursor concentrations during the whole
TMDC growth process. However, the metal−organic precursors
are not only highly toxic and expensive, but are limited to a few
elements, making it challenging for large-scale industrial
applications. Therefore, developing suitable CVD systems with
add-ons especially adapted for TMDCs, which can stabilize the
concentrations of the reactants, are crucial for growing high-
quality (comparable to Scotch-tape-exfoliated ones) and large-
size (up to inch-scale or even larger) TMDCs for practical
applications. At present, chalcogen vapor with a well-controlled
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concentration can be realized by external heating equipment, but
it is difficult to achieve the same level of control for metal sources.
A possible solution is to introduce liquid precursors by peristaltic
pump. In another respect, PECVD and ICP-CVD could be
choices to improve the CVD reaction environments. However,
more creative effort is needed in this direction. In addition, some
other technical innovations, such as using lasers, electric field, or
magnetic field, to precisely control the reaction need to be
sought. For growth mechanism study, more attention should be
paid to the in situ growth and observation techniques, such as in
situ environmental TEM, SEM, optical microscopy, Raman
spectroscopy, PL, mass spectrometry, etc. Such in situ
observations may disclose some key information that cannot
be revealed in a traditional growth process and open a new path
to understanding the growth mechanism of 2D materials.
7.2. Salt-Assisted Growth of TMDCs: A General and Efficient
Route
It has become without doubt that additives in CVD reactions
would bring in some changes in the as-grown 2D materials. Salts,
especially alkali metal halides such as NaCl, KCl, NaBr, and KI,
have been increasingly frequently used to promote the growth of
large size and high quality TMDCs. It is argued that the salts can
react with transition metal oxides, such as MoO3 and WO3, to
form volatile intermediates, which can increase the TMDC
growth rate. Besides deep studies and understanding of the
growth mechanism, we think that the following directions
deserve further exploration in this salt-assisted-growth strategy.
First, a salt-assisted-growth method can be extended to grow
many other 2D materials, such as Te based TMDCs, because Te
has a high melting point of 452 °C and is not easy to sublimate. It
is believed that this salt-assisted-growth strategy may accelerate
the growth of Te based TMDCs as it may increase the activity of
Te. Second, the salt-assisted-growth approach would facilitate
the application of PVD method to grow 2D materials. Materials
with high melting points are not easy to vaporize, which limits
their direct deposition by PVD process. It is possible that the
addition of a certain kind of salt will decrease the melting points
of precursors and make PVD growth facile. Third, salt-assisted
direct growth of metastable phase 2D materials, such as 1T phase
MoS2, without any post-treatment, should be explored.
Considering the fact that ion intercalation into the interlayer of
TMDCs can induce the phase change from 2H to 1T for MoS2, it
is possible to achieve the above goal in the salt-assisted-growth
process. The above-mentioned three areas are just a glimpse of
some potential directions of the salt-assisted-growth strategy,
and more efforts are needed to concentrate on this recently
emerging growth method and achieve controllable growth of
various TMDCs and other 2D materials. We believe that there
are many opportunities ahead.
7.3. High Quality 2D Materials
High quality 2D materials are an everlasting pursuit to satisfy the
demands of high performance electronic and optoelectronic
devices. However, defects are inevitable in current CVD-grown
samples. Although STEM imaging has been widely used to
characterize defects, it is complicated and time-consuming,
making it difficult to be a routine tool. Hence, fast defect
characterization and identification by spectroscopic methods or
optical microscopy imaging are urgently needed. In a further
step, such methods can be considered to be developed toward
high-throughput characterization. Such information can feed
back to the growth experiments quickly and effectively, and guide
improvement of the recipe to grow high quality 2D materials.
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Besides removing or repairing defects, new strategies should be
developed to directly grow high quality 2D materials.
Considering the fact that CVT is a general route to growing
high quality bulk crystals, and many important layered materials,
such as b-P, b-AsP, CrPS4, etc., have been grown by CVT into
bulk forms, currently they cannot be grown into thin 2D flakes
directly by CVD. It is possible that, by conducting further
investigations into the growth thermodynamics and kinetics of
the CVT process, and using it as a reference, we could grow these
interesting layered materials into 2D forms by CVD method.
7.4. Large Single Crystal and Fast Growth Methods: A Long
Way to Go
Recently, numerous efforts have been devoted to the growth of
large single crystals of 2D materials for high-performance and
large-scale device applications. One strategy is to grow single
crystals starting from a single nucleus, while another is to merge
parallel domains. The single nucleus method has been achieved
in graphene growth by using a local feed setup,22 but it is
challenging to transfer this to TMDC growth because of the use
of solid precursors. Nevertheless, combinations of local feeding
with metal−organic precursors or liquid precursors could be a
possible approach to grow large single crystal domains of
TMDCs based on this single nucleus method. On the other hand,
the growth of parallel, oriented domains of TMDCs is limited to
some specific substrates such as c-plane sapphire. The design of
novel substrates for TMDC growth should be extensively
investigated by exploring the characteristic van der Waals
epitaxial growth and chalcogenide chemistry. Following this
consideration, a liquid substrate with a flat surface has emerged as
an ideal platform to reduce the nucleation density, lower the
growth barrier, and obtain large single crystals of TMDCs.
Previously, molten glasses have been used to grow large graphene
and MoS2 monolayer single crystals. However, the transfer
process from the glass is complex and introduces contamination,
which must be avoided. Water-soluble ionic crystals such as NaCl
and KCl, ionic liquids, as well as uniquely designed eutectic salts
may serve as alternative substrates for large single crystal TMDC
growth. In particular, eutectic salts containing Mo or W would be
preferred because they could also be a source of precursor as well
as promoting the growth. It is reasonable to believe that liquid
substrates will greatly promote the scalable growth of TMDCs
and their device applications in the near future.
7.5. Exploration of Novel 2D Materials with Exotic
Properties
Compared with graphene, the exploration of 2D semiconductors
is still in its infancy. Apart from the commonly grown MoS2,
MoSe2, WS2, WSe2, and MoTe2, the design and direct growth of
novel 2D materials are of great importance to cutting-edge
fundamental research and technological applications. Layered
materials such as PtS2, ReS2, Cu2S, Bi2Se3, etc. have been
prepared, and have exhibited unique properties in electronics,
spintronics and valleytronics, phase change, etc. With the rapid
development in computational materials science and the
establishment of materials genome engineering, numerous 2D
materials with exotic properties could be predicted. The
subsequent growth of these novel 2D materials by CVD is an
important direction to pursue. It is worth noting that most
current 2D TMDCs have band gaps in the near-infrared to green
light range, while there are very few 2D materials with band gaps
in the blue light or UV range. There are great opportunities to
further explore 2D materials having band gaps in the blue or UV
range because they are important for certain optoelectronic
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Chemical Reviews
applications. Another feasible way to create novel 2D materials is
to expand the existing 2D material family by properly changing
their elements. For typical MoS2 and MoSe2 crystals, by
selectively stacking different atoms in a monolayer crystal, a
novel “Janus” MoSSe 2D material has been grown and shows
promise for spintronics.55 In addition, a new layered material,
Bi2O2Se, with a high charge carrier mobility and good air stability
has been achieved by replacing selenium with oxygen.348
Therefore, developing novel 2D materials through rational
element substitution is another important direction that needs to
be investigated.
7.6. Low Temperature Growth of 2D Materials for Flexible
Device Applications
As discussed in section 4, the achievement of the low
temperature growth of TMDCs is a very important aspect
toward their use in flexible devices, yet significant challenges
remain. Great effort has been paid to the low temperature growth
of graphene, making the growth temperature as low as around
200 °C. However, such goals have not been achieved for the
growth of TMDCs. In view of the fact that no catalysts are
necessary for TMDC growth, we speculate that some additives
may serve as “pseudocatalysts” to lower reaction barriers and
realize low temperature growth. For example, both MoS2 and
WS2 monolayers with a high crystallinity have been grown at 500
°C by introducing tellurium additives to the CVD growth
process.349 Sodium, potassium, chlorine, and bromine containing
ionic salts have been shown to effectively promote TMDC
growth reactions. However, the temperature is still too high for
most of the polymeric flexible substrates. The following two
points need to be addressed in order to produce CVD-grown
films directly on flexible and transparent substrates: (i) the
development of better “pseudocatalysts” for low temperature
TMDC growth needs collaboration between material scientists
and chemists to modify the reaction paths, and (ii) a search for
polymer substrates that can bear high temperatures is needed.
7.7. Heterostructures: Variations and Easy Growth
As mentioned previously, although vertical heterostructures can
be easily fabricated through a multiple-step aligned transfer
method, this method is time-consuming and residual polymer
and unavoidable contaminants have negative effects on the
properties of as-made heterostructures. An all-CVD method
must be developed for growing high quality vertical hetero-
structures. For lateral heterostructures, because of the critical
requirements of lattice matching, limited types of hetero-
structures such as TMDC/TMDC, graphene/h-BN, and
graphene/TMDC have been currently produced. To extend
this range, not only must advanced growth methods be
developed, but also new 2D materials should be investigated to
grow atomically sharp junctions at the interfaces of the lateral
heterostructures. Very recently, mixed heterostructures have
gained much attention because of the dimensionality-based
properties of the materials. Many of the reported studies, in
which 1D nanowires and 0D QDs are prepared by solution-based
methods, lead to an uncontrollable distribution and poor
uniformity of xD materials on the 2D films. Therefore, the
controlled growth of nanowires, nanotubes, or even QDs that are
uniformly and well-distributed on 2D films is very important to
precisely control the properties of such xD/2D heterostructures.
To broaden the family of 2D material heterostructures, it is
necessary to incorporate other materials, such as g-C3N4 which
has unique photocatalytic properties, as components in the
heterostructures to complement the present TMDC materials.
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Another interesting material is perovskite, which has excellent
optoelectronic properties and demonstrates great potential in
LEDs and solar cells. These new heterostructures may have
improved properties and extend the range of applications.350
The practical application of heterostructures is still at an early
stage and has a long way to go. To date, most state-of-the-art
devices are fabricated from Scotch-tape-exfoliated 2D materials,
which greatly hinders their large-scale production. Large
heterostructures of high quality with clean interfaces and desired
stacking sequences grown by a controllable CVD method are
urgently needed.
7.8. High-Performance Scalable Electronics and
Optoelectronics
Two-dimensional materials are promising for high-performance
electronics and optoelectronics. In the past five years, state-of-
the-art electronic devices with a superior performance, better
than or comparable to conventional silicon, have been fabricated.
However, most of these devices are based on Scotch-tape-
exfoliated 2D materials followed by multiple-step aligned
transfer. The complexities in processing have several disadvan-
tages. First, the process introduces impurities both on the surface
and at the interface of 2D materials, resulting in a decrease in
electron mobility and a degradation of the device performance.
Second, this method cannot be scaled up for practical
applications. Therefore, all-CVD-based material growth tech-
nology is of great importance. Although stacked heterostructures
such as MoS2/WSe2, graphene/h-BN, and MoS2/h-BN have
been grown in one-step or two-step CVD methods, it is still a
challenge for them to be directly integrated into devices. In
addition, all 2D material based electronic devices composed of
MoS2 as channels, h-BN as dielectric, and graphene as electrode
have worked well as FETs. However, they were made by
multiple-step transfer. Therefore, developing advanced CVD
methods to directly grow multiple layers for the simple assembly
of devices is important for achieving scalable electronic and
optoelectronic applications. Another major issue is that, as
mentioned previously, defects exist in CVD-grown 2D materials
and may be major hurdles to realizing high-performance devices
due to the various kinds of charge carrier scattering they cause.
Accordingly, developing simple ways to characterize, engineer,
and repair defects in 2D materials will significantly promote their
application in devices.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: bilu.liu@sz.tsinghua.edu.cn (B.L.).
*E-mail: hmcheng@sz.tsinghua.edu.cn (H.-M.C.).
ORCID
Bilu Liu: 0000-0002-7274-5752
Xiaolong Zou: 0000-0002-3987-6865
Hui-Ming Cheng: 0000-0002-5387-4241
Notes
The authors declare no competing financial interest.
Biographies
Zhengyang Cai received his B.S. degree in materials chemistry from
Wuhan University of Technology in 2012 and a dual degree in computer
science and technology from Huazhong University of Science &
Technology in the same year. In 2015, he received his M.S. degree in
materials science from Wuhan University of Technology. He is now
pursuing his Ph.D. degree at Tsinghua−Berkeley Shenzhen Institute
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Chemical Reviews
(TBSI), Tsinghua University, under the supervision of Prof. Bilu Liu and
Prof. Hui-Ming Cheng. His current research interests mainly focus on
the CVD growth of 2D materials and their heterostructures for
electronics and optoelectronics.
Bilu Liu is currently an associate professor and a core principal
investigator at Tsinghua−Berkeley Shenzhen Institute (TBSI),
Tsinghua University, China. He received his bachelor’s degree in
materials chemistry from the University of Science and Technology of
China (USTC) in 2006, and his Ph.D in materials science from the
Institute of Metal Research, Chinese Academy of Sciences (IMR, CAS)
in 2012. He worked at the University of Southern California (USC) as a
postdoctoral research associate and later as a research assistant professor
between 2012 and 2016. His research interests cover chemistry and
materials science of low-dimensional materials with emphasis on carbon
nanostructures, two-dimensional materials, and their heterostructures.
His work relates to the controlled preparation of these materials and
their applications in electronics, optoelectronics, and catalysis. He has
published 60 papers on these topics with total citations of >7300 and an
H-index of 39.
Xiaolong Zou received his bachelor’s degree in 2006 and Ph.D. in 2011,
both in physics from Tsinghua University. After working as a research
associate at Rice University, Houston, TX, USA, he joined Tsinghua−
Berkeley Shenzhen Institute (TBSI), Tsinghua University, China, as an
assistant professor in 2016. Dr. Zou’s current research focus concerns
the theoretical description of the growth of 2D materials and their
electronic, optical, and catalytic applications.
Hui-Ming Cheng received his Ph.D. in materials science from the
Institute of Metal Research, Chinese Academy of Sciences (IMR, CAS),
in 1992. He has worked at AISTKyushu and Nagasaki University of
Japan, and the Massachusetts Institute of Technology, USA. He is a
member of CAS. He has been professor and founding director of the
Advanced Carbon Research Division at Shenyang National Laboratory
for Materials Science, IMR, CAS, since 2001, and also the founding
director of the Low-Dimensional Materials and Devices Laboratory at
Tsinghua−Berkeley Shenzhen Institute, Tsinghua University, China,
since 2016. His research interests focus on the synthesis and applications
of carbon nanotubes, graphene, other 2D materials, and high-
performance bulk carbons, and on the development of new energy
materials for batteries, electrochemical capacitors, and hydrogen
production from water by photosplitting. He has published more than
550 scientific papers and obtained more than 100 patents.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Nos. 51722206 and 51521091), the Youth
1000-Talent Program of China, the Shenzhen Basic Research
Project (Nos. JCYJ20170307140956657 and
JCYJ20170407155608882), and the Development and Reform
Commission of Shenzhen Municipality for the development of
the “Low-Dimensional Materials and Devices” discipline.
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6133 DOI: 10.1021/acs.chemrev.7b00536

Chem. Rev. 2018, 118, 6091−6133