4040 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO.
10, OCTOBER 2018
CVD Technology for 2-D Materials
Pin-Chun Shen , Yuxuan Lin , Haozhe Wang , Ji-Hoon Park , Wei Sun Leong ,
Ang-Yu Lu , Tomás Palacios , and Jing Kong
(Invited Paper)
Abstract — The urgently growing demand for lowering
the power consumption and increasing the performance
in electronic and optoelectronic systems has been driving
the scientific community to explore new materials and
device architectures. In light of this, 2-D materials including
graphene, hexagonal boron nitride, and transition metal
dichalcogenides have the potential to revolutionize our
semiconductor industry by scaling the devices down to the
atomic level. These materials benefit from several unique
properties, endowed by their 2-D nature, such as surface
free of dangling bonds, ultimate scaling limit in vertical
dimension for almost perfect gate electrostatic control,
and strong excitonic effects. However, to realize the full
potential of these materials, it is required to develop a large-
scale synthesis method. For this, chemical vapor deposi-
tion (CVD) has shown great promise to synthesize these
high-quality 2-D crystals with scalable-production capabil-
ity. In this review, we will give a brief overview of the
current state of the art in CVD growth of 2-D materials and
its prospects for next-generation device applications. First,
we will review several representative growth techniques
in which large area, high quality 2-D materials are demon-
strated. We will then describe the status of the develop-
ment of electronics, optoelectronics, and sensors based
on CVD-grown 2-D materials. Finally, we will discuss the
major challenges and future opportunities in this rapidly
advancing field of research.
Index Terms — 2-D materials, chemical vapour depo-
sition, electronics, graphene, hexagonal boron nitride
(h-BN), optoelectronics, sensor devices, transition metal
dichalcogenides (TMDs).
I. I NTRODUCTION
E VER since the successful exfoliation of graphene in 2004,
2-D materials have attracted enormous attention due
to their unique properties and great potential in various
applications [1]–[3]. In particular, their inherent advantage of
Manuscript received April 23, 2018; revised June 30, 2018 and
August 9, 2018; accepted August 17, 2018. Date of publication August 30,
2018; date of current version September 20, 2018. The authors acknowl-
edge support from the NSF Center for Energy Efficient Electronics
Science (E3S, NSF Grant No. ECCS-0939514), the STC Center for
Integrated Quantum Materials (NSF Grant No. DMR-1231319), AFOSR
FATE MURI (Grant No. FA9550-15-1-0514), NSF DMR/ECCS-1509197,
support from King Abdullah University of Science and Technology under
Contract (OSR- 2015-CRG4-2634), NASA Langley Research Center
(Grant No. NNX14AH11A), and Massachusetts Institute of Technology
Institute for Soldier Nanotechnologies (Grant No. W911NF-13-0001,
T.O.3). The review of this paper was arranged by Editor J. T. Teherani.
(Corresponding author: Pin-Chun Shen.)
The authors are with the Department of Electrical Engineering and
Computer Science, Massachusetts Institute of Technology, Cambridge,
MA 02139 USA (e-mail: pcshen@mit.edu; jingkong@mit.edu).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TED.2018.2866390
0018-9383 © 2018 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
scaling the thickness of a transistor channel down to the
atomic level has shown great potential to extend beyond
Moore’s law [4]. Graphene has been reported to have a
high mobility up to 200 000 cm2 · V−1 · s−1 due to the
linear energy dispersion near the Fermi level, allowing elec-
trons to behave as massless fermions for ultrahigh-speed
electronics [5]. Moreover, the strong light-matter interaction
in the terahertz and mid-infrared regimes makes graphene
a promising platform for novel photonic and optoelectronic
applications [6]. In contrast to graphene, monolayer transition
metal dichalcogenides (TMDs) exhibit intrinsic in-plane asym-
metry, which allows them to show semiconducting properties
with sizable direct bandgaps. Their atomic thicknesses and
large carrier effective masses can offer excellent electrostatic
gate control, a reduced source-to-drain leakage current, and a
higher on-current in the ballistic regime, potentially enabling
ultrascaled devices, tunnel field-effect transistors (FETs), and
ballistic transistors [4], [7], [8]. Besides the channel material
itself, gate dielectric environments and substrates also play
important roles in influencing device performance, since car-
riers scattering could originate from surface roughness, trap
states at interface, and optical phonons. In this regard, hexag-
onal boron nitride (h-BN) can be an ideal candidate due to the
atomic flatness and the dangling-bond-free surface, the large
bandgap, and the relatively high energy of surface optical
phonon modes [9]. Recently, 2-D h-BN has also been used
to modify the work function of metal contacts for reducing
the contact resistance in 2-D electronics [10].
Given that 2-D materials promise a wide range of next-
generation technologies, the capability of controllable, large-
scale synthesis of 2-D materials with high quality and high
yield is essential for their practical applications. Chemical
vapor deposition (CVD), a bottom-up approach, has sev-
eral advantages such as relative simplicity and diversity of
precursors and a fast growth rate, offering a solution for
practical realization of wafer-scale synthesis of 2-D atomic
layers on various substrates. Many reports have demonstrated
high-quality 2-D materials and their heterostructures with scal-
able sizes, controllable thickness, and excellent physical and
chemical properties through CVD techniques, paving the way
to unlock the full potential of 2-D materials.
The aim of CVD growth is to synthesize low-defect
density, large-area 2-D materials with quality comparable
to their exfoliated counterparts and with precise control of
layer numbers, domain size, and morphology. In general,
a CVD process involves excitation of precursors to desired
vaporous phase, transport of reacting gaseous species, and
heterogeneous surface reaction on the substrates, producing
SHEN et al.: CVD TECHNOLOGY FOR 2-D MATERIALS
Fig. 1. Schematic of the growth mechanism of graphene via (a) pre-
cipitation and (b) surface-mediated reaction. (Reprinted with permission
from [14], 2015, Royal Society of Chemistry.)
solid phase materials [11]. Specific CVD techniques such
as low-pressure CVD [12] and plasma-enhanced CVD
(PECVD) [13] have also been employed to improve the homo-
geneity and lower the growth temperature of 2-D materials,
respectively. In this review, we provide a brief overview
of the current state-of-the-art technologies for CVD growth
of 2-D materials including graphene, h-BN, and various
TMDs. Several key parameters for CVD growth of graphene,
h-BN, and TMDs are discussed. We also describe poten-
tial electronic, optoelectronic, and sensing applications of
large-area 2-D materials followed by an outlook for the oppor-
tunities of the system-level integrations of multifunctional
2-D materials. Finally, we briefly comment on the challenges
of bringing 2-D materials and devices to practical applications.
II. G RAPHENE AND H EXAGONAL B ORON N ITRIDE
A typical approach for the CVD growth of graphene or
h-BN is to use the specific precursors either carried by or
mixed with inert gases such as argon or hydrogen, to deposit
these materials on substrates at high temperatures. Many
factors such as metal substrate, precursor, growth temperature,
and pressure are crucial for growths.
A. Effect of Substrate
The substrate greatly affects the growth of graphene and
h-BN. The transition metals were first investigated as cat-
alytic substrates. Many transition metals such as copper (Cu),
nickel (Ni), platinum (Pt), and iron (Fe) have been con-
firmed as suitable growth substrates [15]–[18]. In the case
of graphene, the growth mechanisms depend on the carbon
solubility in the metal. As shown in Fig. 1, for low carbon
solubility metals such as Cu, under typical growth conditions,
carbon atoms tend to directly form single layer graphene on
the surface [14], [15], [19]. For high carbon solubility metals
such as Ni, carbon atoms can dissolve inside the substrate, and
then precipitate to the surface forming a graphite film [20].
Thus, metals with low carbon solubility are more suitable for
monolayer graphene growth, while metals with high carbon
solubility can be used for multilayer graphene growth. The
purity and the roughness of the metal substrate affect the
quality of graphene [21]–[23]. Other than single elemental
metals, alloy substrates with specific carbon solubility are
utilized to suppress precipitation and to attain monolayer
graphene at higher growth rate [24], [25]. Besides, crystalline
orientation of metal substrate has substantial influence on
graphene quality. Cu (111) has a lattice mismatch larger
4041
than 1% with respect to the graphene lattice. Even though
growth process is still considered as epitaxial, the growth
behavior on different crystal facets is different. For example,
the nucleation sites of graphene on Cu (100) show random
orientations [26]. For Cu (111), graphene islands nucleate
with the same crystalline orientation and finally merge into
a continuous film [27], [28].
Similar to graphene, h-BN has honeycomb lattice structure
with alternatively arranged boron atoms and nitrogen atoms.
The growth mechanism of CVD h-BN is similar with graphene
growth. Metal substrates such as Cu and Pt with negligible
solubility of nitrogen lead to a surface-mediated growth mech-
anism and are favorable for monolayer h-BN growth at high
temperature under LP [31]. On the other hand, a substrate such
as Fe foil that possesses high solubility for boron and nitrogen
usually mediates a precipitation growth mechanism and pro-
duces multilayer h-BN. Kim et al. [32] demonstrated that the
large-area multilayer h-BN films with thickness of 5–15 nm
can be grown using Fe foil and borazine as the substrate and
the precursor, respectively [32]. For this precipitation growth
mechanism, the control of the cooling rate is crucial to the
thickness of the as-grown h-BN films [32], [33].
B. Effects of Precursor and Pressure
For graphene growth, methane is used most often, as its
pyrolysis temperature is relatively high which allows the
growth of higher quality material (at higher temperatures).
However, a high growth temperature (1000 °C) limits the
economic efficiency of CVD approach. Thus, other car-
bon source such as benzene and toluene were also uti-
lized to synthesize graphene in low temperature range
(300 °C–400 °C) [34], [35]. In the case of h-BN, the qual-
ity of h-BN highly depends on the precursor and its flow
rate. Solid ammonia borane (BH3 NH3 ) and liquid borazine
(B3 H6 N3 ) are the most commonly used precursors because of
the 1:1 stoichiometry of boron and nitrogen. Fig. 2(a) shows
a schematic of the precursor and the CVD system used for
growing single-layer h-BN. BH3 NH3 is a stable solid and has a
low vapor pressure at room temperature. A pyrolysis process is
required to decompose BH3 NH3 into hydrogen, B3 H6 N3 , and
aminoborane (BH2 NH2 ) [36]. As a liquid precursor, B3 H6 N3
can be delivered to the growth chamber with carrier gas
through a bubbler, though it is a flammable liquid and react
easily with water thus requires more efforts in handling.
The growth pressure also shows a significant effect on the
thickness of h-BN because it affects the concentration of reac-
tants and the rate of mass transport. Song et al. [37] reported
that large-area h-BN films with thicknesses of 2–5 layers can
be grown even on Cu foils under atmospheric pressure (AP).
Also, Jang et al. [38] demonstrated that h-BN films with
various thicknesses can be grown by controlling the partial
pressure of the precursor and the growth time. Typically, a low
partial pressure of B3 H6 N3 can result in monolayer h-BN,
whereas multilayer h-BN with a thickness up to ∼100 nm
can be grown at a high partial pressure of B3 H6 N3 . Wafer-
scale growth of h-BN on Cu with high structural and electrical
uniformity and various thicknesses ranging from 1 to 20
4042
Fig. 2. (a) Schematic of the CVD system used for h-BN growth
with ammonia borane precursor (reprinted with permission from [29],
2013, American Chemical Society). (b) Photographs. AFM images and
Raman spectra of a large-area and uniform monolayer (under LP) and
multilayer h-BN film (under AP). (Reprinted with permission from [30],
2017, American Chemical Society.)
monolayers has been reported using a hybrid LP and APCVD
system, as shown in Fig. 2(b) [30].
C. Wafer-Scale Growth
Wafer-scale growth is essential for future applications
of 2-D materials. Bae et al. [39] developed a roll-to-roll
process to obtain a 30-in large polycrystalline graphene film
grown on Cu substrate. In 2017, Xu et al. [40] reported a
roll-to-roll method to grow meter-size single crystal graphene
after recrystallizing industrial Cu to Cu (111) foil. The most
preferred method for large-area h-BN growth is by using
polycrystalline Cu foil. Wu et al. [40] reported that wafer-
scale monolayer h-BN was grown on a polycrystalline Cu foil
with the size of over 7 in by rolling the Cu foil substrate into
a cylindrical shape under LP. A large-size monolayer h-BN
film of over 25 in was also achieved by winding the Cu foil
substrate into a mainspring shape supported by a multiprong
quartz fork [42].
Polycrystalline h-BN grown on polycrystalline Cu foils
has random crystalline orientations and exhibits a high
density of grain boundary defects. To realize high-performance
IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO. 10, OCTOBER 2018
Fig. 3. Recent progress in wafer-scale graphene and h-BN growth.
Reprinted with permission from [33], [43]–[49].
2-D electronic and optoelectronic devices, synthesis of
large-area and single crystalline h-BN by CVD is highly
demanded. To enlarge the domain size of h-BN grains and
to reduce the grain boundary density or even seamlessly
stitch different domains, one can introduce single crystalline
substrates to allow an epitaxial CVD growth of monolayer
h-BN [43]. By using the epitaxial growth of large-area mono-
layer h-BN on a Cu (111) thin film deposited on a c-plane sap-
phire, highly oriented triangular h-BN grains were achieved,
which finally merged into a continuous film over entire Cu
surface. Synthesis of multilayer h-BN films through epitaxial
CVD growth has also been demonstrated on a 2-in sapphire
substrate. The small difference between the thermal expansion
coefficients of sapphire and h-BN results in a wrinkle-free
growth [44]. Fig. 3 shows the recent progress in wafer-scale
growth of graphene and h-BN.
III. 2-D T RANSITION M ETAL D ICHALCOGENIDES
In the past decade, many strategies have been
demonstrated for large-scale CVD growth of various
TMDs [50]–[58]. Several key factors such as precursor types
and concentrations [59], [60], flow rate of carrier gas, seeding
and growth promoters [61]–[63], and nanoscale morphologies
of substrates [64], [65] show a significant influence on
the resulting TMDs in terms of morphology, domain size,
uniformity, and electrical performance. In this section, such
several crucial parameters are reviewed.
A. Effects of Precursor and Seed
In 2012, Liu et al. [66] adopted a two-step process of dip
coating/sulfurization to grow large-area MoS2 films on SiO2 /Si
and sapphire substrates using ammonium thiomolybdate
[(NH4 )2 MoS4 ] solution. A high-temperature annealing process
(500 °C–1000 °C) was employed to trigger the thermolysis of
(NH4 )2 MoS4 , resulting in bilayer and trilayer MoS2 sheets.
The presence of oxygen during the conversion process shows
a significant impact on the quality of the as-grown MoS2 .
The MoS2 sheet grown on a chemically inert substrate sap-
phire generally exhibited higher crystalline quality (stronger
Raman and photoluminescence intensities) than that grown
SHEN et al.: CVD TECHNOLOGY FOR 2-D MATERIALS
Fig. 4. Brief overview of the progress made in CVD growth of TMDs, including single crystals, monolayer and multilayer continuous films, vertical
and in-plane heterostructures, superlattcies, and Janus monolayers. All reprinted with permissions.
on SiO2 /Si. The authors suggested that the oxygen from
SiO2 could affect the thermal decomposition of (NH4 )2 MoS4
during the high-temperature process, and thus degrade the
quality of the as-grown MoS2 . It was also found that the
electron mobility of the as-grown MoS2 films was improved by
two orders of magnitude (from 0.02 to 4.7 cm2 · V−1 · s−1 )
after annealed in the presence of sulfur vapor. A similar
improvement in MoS2 electron mobility by sulfur treatment
was also observed from exfoliated samples [67].
Besides the solution-based precursor, there is another two-
step method for large-area TMD growth, in which a thin
film of solid metals or metal oxides is first deposited on
the target substrates, and then a sulfurization/selenization/
tellurization process is employed to obtain the desired TMD
thin films [52], [56]–[58], [68], [69]. Zhou et al. [52], [58]
revealed that the phases of the as-grown MoTe2 highly depends
on the chemical composition of the Mo sources. In their
growth, the tellurization of MoO3 precursor in a sufficient
tellurium atmosphere resulted in semiconducting 2H-MoTe2
with p-type conduction and a field effect hole mobility of
1 cm2 · V−1 · s−1 , but a metallic 1T’ phase was obtained when
Mo was used as the source. The abovementioned two-step
method is simple and scalable, but the MoS2 thin films
grown by this approach usually suffer from a low electron
mobility (0.004–0.8 cm2 · V−1 · s−1 ) [56], [57]. The lack of
controllability of the thicknesses and uniformity over a large
area also limits the quality of this synthesis method.
On the other hand, vaporous-phase reactions of TMD
synthesis either by thermal excitations of metal oxide
powders (e.g., MoO3 or WO3 ) and chalcogen elements
(e.g., S or Se) or metal-organic and organic compound sources
[e.g., molybdenum hexacarbonyl Mo(CO)6 and diethyl sul-
phide (C4 H10 S)] has been widely adopted to prepare highly
4043
crystalline TMD single crystals, control the shapes or edges of
the as-grown TMDs, and produce diverse TMD heterostruc-
tures. Taken MoS2 as an example, it is proposed that the
reaction is simply completed by two steps [70]
MoO3 + x/2S → MoO3−x + x/2SOx (1)
MoO3−x + (7 − x)/2S → (3 − x)/2MoS2 . (2)
During the reactions, the variations of the local precursor
concentrations along the growth substrates remarkably influ-
ence the shapes and the edge terminations of the as-grown
TMD grains [60], [71], [72]. It has been suggested that three-
point-star shaped MoS2 is favorably synthesized in a low-
temperature or sulfur-rich condition due to the significant
mismatch between the growing rates of Mo-zigzag termi-
nation and S-zigzag termination (rate of the Mo edge is
three times faster than that of the S edge). As a result,
the edges of the three-point-star domain are proposed to
be S-zigzag terminated. In contrast, a Mo-rich or high-
temperature environment would produce truncated triangles,
in which the edges are composed of both Mo- and S- zigzag
terminations. Dendritic-like grains can be observed in a non-
equilibrium growth condition when a high carrier gas flow rate
is employed, leading to a facilitated mass transfer process and
an increased growth rate. Metal halide MoCl5 has also been
used as a precursor to grow large-area monolayer and few-
layer MoS2 films [73], [74]. The chemical reaction between
MoCl5 and S was suspected to be a one-step process during
which no intermediate byproducts such as MoO2 and MoOS2
were formed [59]. The as-grown MoS2 films showed good
continuity and uniformity. However, the reported electron
mobility is only 0.003 − 0.03 · cm2 · V−1 · s−1 [73].
In addition to precursors, seeding promoters play a
critical role in laterally enlarging the growth area of TMDs.
4044 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO. 10, OCTOBER 2018
Lee et al. [16] reported that by introducing graphene-like
molecules such as graphene oxide, perylene-3,4,9,10-
tetracarboxylic acid tetrapotassium salt (PTAS), and
perylene-3,4,9,10-tetracarboxylic dianhydride coated on
growth substrates, large-area MoS2 layers can be grown at a
relatively low temperature under ambient conditions [61]. The
density (or concentration) of the seeding promoters exhibits
a significant effect on the MoS2 nucleation density. A high
seed density usually results in a high nucleation density
on the growth substrate, where MoS2 flakes can merge to
form a continuous film. The presence of seeding promoters
possibly increases the surface adhesive force of MoS2 and
lowers the free energy barrier of the nucleation. [62]. These
two factors together facilitate the large-area layered growth
of MoS2 and decrease the required growth temperature. The
seeding-promoter-assisted growth technique also enables the
direct growth of monolayer MoS2 on diverse substrates such
as Au, h-BN, and graphene. In addition to spin coating
the seeding promotor on the growth substrate before the
synthesis, it was found that other types of seeding promotors
can be used, and methods such as thermal evaporation or
diffusion [75], [76] onto the growth substrate during the
synthesis from upstream also result in facilitated MoS2
growth. PTAS seeding promoter has also been used for other
TMD growth including WS2 and MoSe2 [53], [77], [78].
Rather than using solid powders as precursors,
metal-organic CVD (MOCVD) relies on gaseous sources.
Typically, the metal-organic and organic compound sources
are first heated to vaporous phase and then released into a
reaction chamber with well-controlled ratios through mass
flow controllers. The molecules are decomposed in the
chamber by thermal energy and the desired atoms can be
deposited onto the target substrates atom by atom through
surface diffusion. Therefore, the MOCVD method allows
precise controls of the concentrations of both metal and
chalcogen precursors during the growth, providing atomic
scale high-quality deposition. 4-in wafer-scale, monolayer
MoS2 and WS2 films on SiO2 /Si substrates have been
demonstrated by Kang et al. [79]. The MOCVD-grown TMD
films exhibited excellent morphological homogeneities in
terms of domain sizes and thicknesses. The MoS2 transistors
showed high electron mobility of 30 cm2· V−1 · s−1 at room
temperature and 114 cm2 V−1 s−1 at 90 K. While this work
has demonstrated wafer-scale growth of high-quality TMD
films, more efforts are still needed to enlarge the grain size
of the films for high-performance device applications. Several
factors including H2 gas, halide salts (e.g., NaCl), water,
growth temperatures, and precursor ratios show significant
impact on the morphology, the reproducibility, and the
coverage of the MOCVD growth [79]–[81].
B. Effect of Substrate
Substrates also play a decisive role in the TMD growth.
In general, the epitaxy of TMD atomic layers is highly
sensitive to the nanoscale morphology, terminating atoms,
and lattice constant and symmetry of the growth substrates.
It has been revealed that the shapes of MoS2 flakes are
highly sensitive to the lattice symmetry of the substrates.
Triangular MoS2 single crystals with sharp edges are usually
found on SiO2 /Si or silicon nitride (Si3 N4 ) [82] substrates,
but a SrTiO3 substrate with quartic symmetry can produce
dendritic MoS2 flakes with threefold symmetry [83], [84],
as a result of the anisotropic diffusion of precursors on the
substrates. Furthermore, MoS2 crystals with six-fold symmetry
were grown by using silicon carbide (0001) as the substrates
where the lattice is naturally six-fold symmetric [85].
To realize high-quality van der Waals (vdW) epitaxy
of TMDs, an atomically flat and chemically inert surface
with hexagonally arranged in-plane lattice is required. Var-
ious substrates such as mica [64], sapphire [57], [65], [86],
h-BN [87], [88], and graphene [74], [89], have been used for
large-area vdW epitaxy of TMDs. Ji et al. [64] reported that
centimeter-scale uniformly aligned MoS2 monolayer flakes
with similar domain sizes can be grown on mica [64]. Accord-
ing to their statistics, a larger average domain size corre-
sponds to a lower surface nucleation density, suggesting that
the nucleation density, rather than the spreading ability of
Mo-S species on mica, controls the size of MoS2 flakes.
Dumcenco et al. [65] reported that as high as 91.5% of the
single-crystal MoS2 domain on the c-plane sapphire are well
aligned with dominant edge orientations of 0° and ±60°,
significantly reducing the density of grain boundaries in the
film. The weak vdW interaction between MoS2 and sapphire
allows MoS2 nuclei a certain extent of rotation and translation
with respect to the sapphire surface in the initial growth
stage until they find the most stable configuration with the
substrate. The field-effect mobility of the as-grown MoS2 film
reached ∼25 cm2 ·V−1 s−1 and was independent of the channel
length (4–80 µm). In addition to rigid insulating substrates,
Shi et al. [90] revealed that the monolayer MoS2 growth is
sensitive to the crystallography of Au foils. At relatively
high temperatures, large-domain single-crystal MoS2 grains
(∼115 µm) are more preferentially grown on Au (100) and
Au (110) facets than on Au (111). This facet-dependent
growth behavior originates from the binding energy differences
between the substrate facets and MoS2 . These works demon-
strated the good controllability of the domain size and the
orientation through vdW epitaxy and the substrate-facet effect,
which is a significant step toward scalable growth of low-
grain-boundary density, large-domain TMD films. Techniques
for identifying the TMD crystal orientations and resolving
the grain boundaries through second-order nonlinear optical
interactions have also been developed [76].
Direct CVD growth of 2-D materials on flexible polymer
substrates is essential for scalable fabrication of 2-D flexible
devices. However, no polymer substrate would be ther-
mally stable at the typical CVD growth temperatures
(600 °C–900 °C). Recently, progress has been made to
overcome this challenge by using the PECVD [13] or
wisely selecting a precursor with a low decomposition
temperature [71]. The presence of accelerated energetic elec-
trons, excited molecules and atoms, and other highly active
species in the PECVD [91] lowers the reaction energy barrier
and hence decreases the required temperature for growth
of the target materials. Ahn et al. [13] demonstrated that
SHEN et al.: CVD TECHNOLOGY FOR 2-D MATERIALS
large-area multilayered MoS2 (3–4 nm in thickness) thin
films can be grown on polyimide substrates at as low as
150 °C–300 °C using a Mo-deposition/sulfurization PECVD
approach [13]. The as-grown MoS2 showed average mobilities
of 2–3.71 cm2 · V−1 · s−1 , which is higher than those of the
MoS2 thin films grown by conventional CVD processes using
a similar two-step approach [56], [57], likely due to a higher
crystalline quality and no transfer processes involved. Mono-
layer MoS2 single crystals (>100 µm) grown on polyimide
substrates at a low temperature of 450 °C has also been
achieved by using (NH4 )2 MoO4 as the precursor [71].
In addition to the effects on shape and morphology, recent
study has revealed that the underlying substrates can induce
unintentional doping and strain in the as-grown TMDs [92].
Theoretical investigation has also shown the formation energy
of sulfur vacancies could highly depend on the types (tensile
or compressive) and the strength of the strain imposed on
the TMDs [93], [94]. For example, sulfur vacancies become
energetically less favorable when a tensile strain is intro-
duced into the MoS2 lattice. This finding paves the way to
grow low-defect-density TMDs for high-performance appli-
cations. Moreover, substrate-driven band structure modulation
of and brightening of dark excitons in WSe2 through strain-
engineered growth has also been reported [95].
C. Large-Scale Growth of TMD Single Crystals
An approach to obtain grain-boundary free TMD atomic
layers is through large-scale growth of single-crystal TMD
grains. Chen et al. [96] demonstrated that by introducing an
optimal amount of oxygen during the growth, large triangular
monolayer MoS2 with the side length of up to 350 µm can
be grown on a c-plane sapphire, with a lateral growth rate
of ∼12µm min−1 . The presence of oxygen in the growth
environment plays three critical roles.
1) Preventing the sulfurization of the MoO3 source so that
a continuous evaporation of MoO3 during growth is
guaranteed.
2) Behaving as an etching reagent that removes unsteady
nuclei either on the MoS2 surface or on the substrate,
making the edges the only reactive sites to laterally
enlarge the domain size.
3) Chemically etching the MoS2 edges and then converting
Mo and S atoms to MoO3 and SO2 gas molecules.
During the oxygen-assisted growth, the growth and etch rates
are competing with each other. An optimal balance between
growth and etching through carefully tuning the growth time
is required to obtain the large domains of single crystals. The
FET based on the as-grown MoS2 exhibited n-type conduction
with electron mobility of as high as 90 cm2· V−1 · s−1 and
ION /IOFF ratio of >107.
Halide salts (e.g., NaCl and KCl) also play a critical
role in synthesizing large-area single crystals. The introduced
halide salts can react with Mo or W precursors, forming
active gaseous oxyhalide species (e.g., MoOCl4 and WOCl4 ).
The presence of the oxyhalide species greatly facilitate the
reaction and lowers the growth temperature [63], [97], [98].
The usage of these catalytic salts is especially important for
growing large-scale transition-metal tellurides because of the
4045
low reaction activity of Te [54]. Large TMD crystals including
WS2 (200 µm), WSe2 (140 µm), MoTe2 (1 mm), and WTe2
(350 µm) have been achieved based on this halide-salt-assisted
growth method [63], [97].
D. Concurrent Synthesis
Recently, Sun et al. [99] demonstrated a new configuration
of CVD method that allows concurrent synthesis of various
monolayer TMDs at once in the same single-zone furnace.
MoO3 and WO3 were first spread onto two separate groups of
growth substrates and were vertically put in the CVD chamber.
In this approach, both the vertically placed substrates and the
rich sulfur environment play key roles. Molecular dynamics
simulation revealed that because there is one order of mag-
nitude larger partial pressure of sulfur flowing on the top of
those vertical substrates, MoO3 and WO3 precursors are well
confined in space between two adjacent standing substrates,
which guarantees that no alloy (MoxW1−x S2 ) will be formed.
Their monolayer MoS2 and WS2 transistors exhibited electron
mobilities of 64 and 21 cm2 V−1 · s−1 , respectively, which is
comparable to the values reported by MOCVD [79].
E. Layer-Controlled and Patterned Growth
Since TMDs have rich layer-dependent properties, the large-
area preparation of multilayer TMD crystals or films with
controllable thicknesses has also been intensively studied [40],
[52], [58], [100]. It has been shown that by treating the
SiO2 /Si substrates with oxygen plasma for different periods,
scalable MoS2 films with controlled thicknesses (monolayer,
bilayer, and trilayer) can be synthesized [100]. The as-grown
multilayer films exhibited uniform thicknesses with field effect
mobility values of 3.6, 8.2, and 15.6 cm2 · V−1 · s−1 for
the mono-, bi-, and trilayer MoS2 transistors, respectively.
The plasma treatment lowers the surface energy of the SiO2
substrate by forming Si-O or Si-OH dangling bonds on
the surface, making the surface hydrophilic and providing
a higher surface reactivity. It was proposed by the authors
that this facilitates the heterogeneous nucleation and layer
growth rates of MoS2 . In fact, patterned growth of TMDs
and their heterostructures can be also realized by employing
oxygen-plasma technique [101], [102]. This method would
enable direct growth of TMDs on other high-k dielectrics with
controllable thicknesses for electronic applications.
F. 2-D Heterostructures
The 2-D heterostructures with various combinations and
energy band alignments are the building blocks toward a
wide range of high-performance 2-D technologies such as
1-D contacts [103], tunneling FETs (TFETs) [104], [105],
and p-n-junction [106], [107] for next-generation electron-
ics and optoelectronics. Although 2-D heterostructures
can be achieved by physically pick-up-and-transfer met-
hod [103], [108], CVD allows the direct growth of lattice
aligned TMDs layers for both vertical heterojuctions with
clean interfaces [89], [87], [109] and seamlessly 1-D lateral
heterostructures with atomically sharp interfaces [110], [111].
4046
Fig. 5. Summary of band gaps (Eg in eV) of various 2-D materials
and corresponding electronic functional components and optical spectra
associated with each band gap range.
By using the PTAS-diffusion-assisted method, Ling et al. [75]
demonstrated that a variety of large-area 2-D heterostuctures
(e.g., MoS2 /WS2 , MoS2 /graphene, and MoS2 /h-BN) can be
synthesized regardless of the lattice mismatch between the
materials. The as-grown heterostuctures exhibit an in-plane
“parallel stitched” configuration at the junction [75]. Complex
multiheterostructures (e.g., WS2 -MoSe2 -WSe2 ) and superlat-
tices (e.g., WS2 -WSe2 -WS2 -WSe2 -WS2 ) have also been real-
ized through edge-epitaxy growth [112], [113]. The as-grown
monolayers share the same crystal orientation and seamlessly
bond at the interfaces. Atomically sharp interfaces existing
between each monolayer domain has been confirmed through
high-angle annular dark-field scanning transmission electron
microscope [113]. Recently, Janus monolayer MoSSe, a new
TMD structure with out-of-plane asymmetry in which the top-
layer S atoms are fully replaced with Se atoms, has also been
demonstrated [114].
IV. D EVICE A PPLICATIONS W ITH CVD 2-D M ATERIALS
The strong covalent bond in plane and the weak vdW
interactions in between planes of 2-D materials give rise to
a high degree of mechanical stability and flexibility. The
bandgap of 2-D materials spans from 0 eV in the case
of monolayer graphene, all the way to around 6 eV in
the case of h-BN (Fig. 5). Such a diversified functional-
ity and their unique electronic and optoelectronic properties
make 2-D materials highly suitable for a wide range of
applications, from high performance transistors, to extremely
sensitive photodetectors and sensors. In addition, the lack
of dangling bonds in 2-D materials have not only enabled
many complex heterostructure devices with almost perfect
interfaces, but also made it easy to be integrated to any
other materials or technologies. In this section, we focus on
potential electronic, optoelectronic and sensing applications
based on 2-D materials and discuss about the opportunities and
challenges of the system-level integrations of multifunctional
2-D materials and other conventional technologies boosted by
CVD synthesis technologies.
The 2-D semiconductors such as MoS2 and WSe2 offer
promising opportunities to advance the state-of-the-art elec-
tronics, for multiple reasons. First, the good crystallinity and
mechanical flexibility make CVD 2-D semiconductors a good
IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO. 10, OCTOBER 2018
candidate for next-generation flexible electronics [1], [115].
FETs based on 2-D semiconductors, such as MoS2 , WSe2 ,
and MoTe2 showed good mobilities and high ION /IOFF cur-
rent ratios [116]–[118], with which single-stage and multi-
stage logic circuits based on NMOS and CMOS technologies
[16], [46], [119], [120], as well as radio frequency analog
circuits [121]–[123] were implemented. Second, the atom-
ically thin nature and the lack of surface dangling bonds
in 2-D- semiconductors are ideal for ultrashort and ultra-
thin body (UTB) transistors to reach the ultimate limit for
scaling [1], [124]. Multiple reports showed that many short-
channel effects, such as drain-induced barrier lowering, direct
source–drain tunneling, and surface roughness scattering of
UTB could be greatly reduced in TMD based short channel
FETs [1], [124]–[126]. Third, the perfect interfaces in
2-D heterostructures, as well as the relatively large band gap
and effective mass of semiconducting TMDs make a perfect
match for TFETs in low-power applications [127], [128].
Nevertheless, due to the immatureness of the synthesis, and
process technology, it has been very challenging to improve
the yield and scale up the complexity of 2-D semiconductor-
based circuits. In order to address this issue, Ling et al. [75]
and Yu et al. [119], [129] proposed an end-to-end design flow
that allows rapid optimization of material synthesis, device
technology and circuit layout/design to ensure maximum sys-
tem yields. With high quality CVD MoS2 , optimized process
technology, and specifically designed logic gate geometry,
it is estimated that the complexity of the logic circuits made
with MoS2 transistors could be as high as 104 with >95%
yield. As a system level demonstration, Wachter et al. [130]
demonstrated a 1-bit microprocessor consisting of 115 tran-
sistors CVD MoS2 FETs with around 80% fully functional
algorithmic logic unit and implemented simple instruction sets.
Graphene-based photodetectors in the infrared range have
shown great promise in next generation image sensor [131]
and optical communication [132], [133] applications, mainly
because of the discoveries of multiple novel photodetection
mechanisms [6], and its facile integration with other electronic
or photonic systems. For instance, Goossens et al. [131] fab-
ricated graphene-colloidal quantum dots photogating detector
arrays directly onto a CMOS readout integrated circuit chip
and demonstrated a monolithically integrated 388 pixel by
288 pixel graphene-CMOS image sensor chip in visible,
near IR and short-wave IR ranges. Lin et al. [133] integrated
graphene with chalcogenide glass-based photonic components
and demonstrated fully functional photonic devices such
as on-chip polarizers, thermos-optic switches, and mid-IR
photodetectors and modulators. In addition, the sizes of
many macroscopic optoelectronic applications are typically
on the order of millimeters to centimeters, which would
not be possible if no large-scale synthesis method has
been developed. Researchers have attempted to incorpo-
rate CVD graphene-based transparent electrodes into solar
cells [134], [135], organic LEDs [134], [136]. TMDs have
also shown great potential in many macroscopic applications
such as solar cells [137], [138] and LEDs [139]. For example,
due to the high absorption coefficients of 2-D semiconducting
TMDs, it was found that graphene/TMD heterostructures and
SHEN et al.: CVD TECHNOLOGY FOR 2-D MATERIALS
TMD/metal stacks, when properly designed, could absorb
almost 100% of the solar spectrum even when the TMD
absorbing layers are less than 20 nm [137], and the power
density of up to 2.5 MW/kg could be achieved, which cor-
responds to 1–3 orders of magnitude higher than the state of
the arts.
Graphene and other 2-D materials are fundamentally advan-
tageous for gas, chemical and biological sensing, because
of the large specific surface areas and strong, but relatively
reversible surface activities enabled by their low dimen-
sionality and weak vdW interlayer interactions. In addi-
tion to the exposed electron gas on 2-D crystals that could
attract and interact directly with many analytes [140], [141],
defects and impurities such as sulfur vacancies in MoS2 ,
and B, S or Al substitutes in graphene could be more
sensitive to certain molecules [142], [143]. The physically
adsorbed or chemically bonded analytes would then mod-
ify the electrical [143], [144], optical [141], [145], [146], or
electrochemical [144], [147] properties of the sensing mate-
rial, leading to a signal transducing process. Although the
charge-transfer-based sensing mechanism is very universal,
there have also been tremendous efforts to address some cru-
cial issues, such as selectivity [144], [147], reliability [148],
and scalability [149], to push the 2-D material based sensing
systems toward real applications.
V. C HALLENGES
The key technological issues to essentially realize the afore-
mentioned vision include reliable transfer processes preserving
intrinsic properties of 2-D materials, ohmic contacts, and
controllable doping for modification of polarity and conduc-
tivity. Since 2-D materials are atomically thin, any surface
contamination or interface impurities may lead to a dramatic
change of their physical properties, such as unintentional
doping [150], [151], interface charge scatterings [106], and
degraded contact resistance [152].
A. Transfer
Large-area 2-D materials including graphene, h-BN, and
TMDs have been successfully synthesized through CVD
methods on either transition metals (e.g., Cu, Ni, Pt, and
Au) or insulating substrates including SiO2 and sapphire.
To achieve high-performance devices for various applications
including biosensors, FETs and flexible electronics, it is
important to develop a reliable technique to transfer large-area
2-D materials with minimal damage and contamination and
onto arbitrary substrates. In this section, we will discuss the
current challenges in transferring large-area 2-D materials in
two main categories: wet and dry transfer approaches.
1) Wet Transfer: Considering yield and cost, Cu-catalyzed
CVD is among the most promising approaches to obtain
large-area graphene for industrial applications. The major
stumbling block in using CVD graphene grown on Cu is
that multiple defects randomly generated in graphene during
the polymer-assisted transfer process. The defect can be as
serious as centimeter-scale cracks or as tiny as nanometer-
tall wrinkles. The transfer process also leaves many polymer
4047
residues on the graphene surface which acts as charge scatter-
ing centers. Furthermore, although Cu or Ni as catalytic sub-
strates for CVD grown graphene can be effectively removed
by the common etchants such as iron nitrate, iron chloride and
ammonium persulfate, the transferred graphene samples were
contaminated by metal particles from the aqueous etchants.
These metal particles could not be easily washed by clean
water which has been confirmed by time-of-flight secondary
ion mass spectrometry [153] and Raman spectroscopy [154].
All these defects and contaminants trigger charged impurity
scattering and degrade carrier transport in graphene limiting
the performance of graphene devices. Nevertheless, the trans-
fer process is unavoidable for most of the foreseen applica-
tions. The situation becomes more challenging if the targeted
substrates are hydrophobic or rough. The use of liquid with
small surface tension [155] and polymer with large elastic
modulus [156], [157] have been proposed to overcome the
prior and latter issues, respectively, but thus far, no sin-
gle process can concurrently solve all issues. Hence, more
research efforts are needed to develop a reliable approach to
transfer the one-atom-thick graphene film to arbitrary sub-
strates with minimum carrier scattering centers (e.g., surface
contamination and nanosized wrinkles.). The same problems
happened on hBN films synthesized on transition metals.
Instead of metal etchants, hydrofluoric acid [158] or
diluted alkaline solution [56] is used to detach TMD films
from the insulating growth substrates (i.e., SiO2 or sap-
phire). This transfer approach is not perfect and results
in many issues such as TMD material degradation, poly-
mer and etchant residuals [159], [160], limiting the per-
formance of TMDs. Thanks to the weak van der Waals
interactions between TMDs and the growth substrate, TMDs
have been transferred using etching-free direct delamina-
tion methods [69], [108], [160]–[162]. One of these strate-
gies is to induce sufficient force to delaminate MoS2 film
by ultrasonication-generated microbubbles at the interface
between MoS2 and the substrates [160]. On the other hand,
TMDs can also be directly delaminated via capillary force in
water due to the hydrophobicity of a polystyrene [163] or a
polydimethylsiloxane (PDMS) [164] supporting layer.
To reuse expensive catalytic substrates such as Pt, Au, and
Ir, electrochemical delamination method has been considered
as a nondestructive approach to separate graphene/h-BN from
the metal growth substrates, without dissolving it. The electro-
chemical delamination method is also called “bubble transfer,”
which generates hydrogen bubbles between graphene and the
metal substrates to weaken the adhesion at the interface in
dilute alkaline solutions [165], but this process can induce
mechanical damage [166] to monolayer 2-D materials which
need to be addressed in the future.
2) Dry Transfer: Electronic applications, including solar
cells, light-emitting diodes, touch screen technology, photode-
tector devices, and membranes, generally require large-area
2-D materials to be transferred onto hydrophobic flexible or
soft substrates, and the above-mentioned wet transfer methods
cannot serve the purpose. In Year 2013, Song et al. [167]
developed a dry transfer technique that allows CVD graphene
to be transferred with high fidelity at predefined location
4048 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO. 10, OCTOBER 2018
on most of the surfaces, including hydrophobic and frag-
ile polymer thin films, with the use of a “self-releasing”
polymer interlayer between a PDMS elastomer stamp and
graphene. In the same year, Martins et al. [168] reported a
lamination method that can directly transfer graphene onto
various flexible substrates, including polytetrafluoroethylene
filter membranes, polyvinyl chloride, polycarbonate, paraffin,
paper, and even clothes. Most reported dry transfer techniques
rely on heat (100 °C–180 °C) to ensure proper adhesion
between the 2-D film and destination surface [135], [169].
In the event of heat- or moisture-sensitive substrates, a
room-temperature dry-transfer technique is recommended for
stacking 2-D materials on them [135]. Besides that, to build
functional blocks solely made of 2-D materials, it is important
to vertically stack different 2-D materials at desired location,
and which has recently been demonstrated with the fabrication
of centimetre-scale van der Waals heterostructures of TMD
films, using a programmed vacuum stack approach [108].
B. Doping
Controllable chemical doping is another crucial aspect
of process technologies. Because of the 2-D nature and
the resulting high surface-to-volume ratio, many surface
treatment methods are very effective to achieve decent
amounts of doping, most of which are physisorption. Such
physisorbed dopants could be introduced through gaseous
or liquid phase treatment [170], [171], molecular surface
adsorption [172], dipole or residual charge from surround-
ing dielectrics [173]–[177]. However, dopants introduced by
physisorption are usually unstable, since no chemical bonding
is formed. Therefore, more efforts should be made to achieve
effective doping through synthetic strategies such as chemical
functionalization or substitution, for instance, chlorination of
graphene induced through plasma treatment [178] or pho-
tochemical reaction [179], which give rise to an efficient,
nondestructive, and air-stable p-type doping. In terms of
MoS2 , oxygen passivation on the naturally existing sulfur
vacancies was both predicted theoretically and observed exper-
imentally to introduce p-type doping [180]; Nb and P were
found to be effective p-type substitution dopants in MoS2
that could be introduced during synthesis or through plasma
treatment [181], [182].
VI. C ONCLUSION
Over the past few years, substantial progress in scalable
CVD growth and applications of atomically thin 2-D materials
has been made. Before bringing them into real products,
there are still several important challenges ahead. A better
comprehension of growth mechanisms is primarily necessary.
In addition, a deep understanding of defect physics and sur-
face chemistry of the 2-D materials and developing effective
methods to characterize the nanoscale defects in 2-D crystals
play critical roles in engineering the natures of 2-D materials
and exploring new atomically layered materials. If the growth
of large-area and high-quality 2-D materials with high control-
lability and reliability can be developed, 2-D materials could
enable a new era for the semiconductor industry.
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Pin-Chun Shen received the B.S. degree in
chemical engineering and the M.S. degree in
photonics and optoelectronics from National Tai-
wan University, Taipei, Taiwan, and the M.S.
degree in electrical engineering and computer
science from the Massachusetts Institute of
Technology, Cambridge, MA, USA, in 2017,
where he is currently pursuing the Ph.D. degree
in electrical engineering and computer science
with Prof. J. Kong.
Yuxuan Lin received the B.S. degree in micro-
electronics from Tsinghua University, Beijing,
China. He is currently pursuing the Ph.D. degree
with the Department of Electrical Engineering
and Computer Science, Massachusetts Institute
of Technology, Cambridge, MA, USA, under the
supervision of Prof. Tomás Palacios and Prof.
Mildred Dresselhaus.
His current research interests include synthe-
sis, characterizations, and optoelectronic appli-
cations of 2-D materials.
Haozhe Wang received the B.S. degree from
Shanghai Jiao Tong University, Shanghai, China,
in 2012, and the M.S. degrees (two dual-master
program between U.S. and China) from North-
western University, Evanston, IL, USA, in 2014,
the Georgia Institute of Technology, Atlanta, GA,
USA, in 2015, and Shanghai Jiao Tong Univer-
sity, in 2015. He is currently pursuing the Ph.D.
degree with Prof. Jing Kong with the Depart-
ment of Electrical Engineering and Computer
Science, Massachusetts Institute of Technology,
Cambridge, MA, USA.
His current research interests include graphene and boron nitride
growths and their applications.
IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 65, NO. 10, OCTOBER 2018
Ji-Hoon Park received the Ph.D. degree in
physics from Sungkyunkwan University, Suwon,
South Korea, in 2014.
He is currently a Post-Doctoral Research
Fellow with the Research Laboratory of Elec-
tronics, Massachusetts Institute of Technology,
Cambridge, MA, USA. His current research
interests include synthesis and characterization
of 2-D materials by chemical vapor deposition
and metal-organic chemical vapor deposition.
Wei Sun Leong received the B.Eng. (∗ 1 Hons.)
degree in electrical engineering from Univer-
sity of Technology Malaysia, Malaysia, in 2011,
and the Ph.D. degree in electrical and com-
puter engineering from the National University of
Singapore, Singapore, in 2015.
She is currently a Post-Doctoral Associate
(with Prof. Jing Kong) with the Department
of Electrical Engineering and Computer Sci-
ence, Massachusetts Institute of Technology,
Cambridge, MA, USA. Her current research inter-
ests include the interface of nanofabrication, device physics, and materi-
als science to understand and engineer 2-D materials-based electronic
devices.
Ang-Yu Lu received the B.S. and M.S. degrees
in engineering and system science from National
Tsing Hua University, Hsinchu, Taiwan. He is cur-
rently pursuing the Ph.D. degree with the Depart-
ment of Electrical Engineering and Computer
Science, Massachusetts Institute of Technology,
Cambridge, MA, USA.
His current research interests include chemical
vapor deposition synthesis and characterization
of graphene, hexagonal boron nitride, and Janus
transition metal dichalcogenide monolayers.
Tomás Palacios received the Ph.D. degree from
the University of California, Santa Barbara, CA,
USA, in 2006.
He is currently a Principal Investigator with
the Department of Electrical Engineering and
Computer Science, Massachusetts Institute of
Technology (MIT), Cambridge, MA, USA. His
current research interests include demonstrat-
ing new electronic devices and applications for
materials such as graphene and gallium nitride.
He is the Founder and the Director of the MIT/
Microsystems Technology Laboratory Center for Graphene Devices and
2-D Systems.
Jing Kong received the B.S. degree in chemistry
from Peking University, Beijing, China, in 1997,
and the Ph.D. degree in chemistry from Stanford
University, Stanford, CA, USA, in 2002.
She is currently the Associate Director of
Microsystems Technology Laboratory and a Prin-
cipal Investigator with the Research Laboratory
of Electronics with the Massachusetts Institute of
Technology (MIT), Cambridge, MA, USA.