1 s2.0 S2589004221011974 Main

iScience ll
OPEN ACCESS
Review
Salt-assisted chemical vapor deposition
of two-dimensional transition metal dichalcogenides
Shisheng Li1,*
SUMMARY
Salt-assisted chemical vapor deposition (SA-CVD), which uses halide salts (e.g.,
NaCl, KBr, etc.) and molten salts (e.g., Na2MoO4, Na2WO4, etc.) as precursors,
is one of the most popular methods favored for the fabrication of two-dimen-
sional (2D) materials such as atomically thin metal chalcogenides, graphene,
and h-BN. In this review, the distinct functions of halogens (F, Cl, Br, I) and alkali
metals (Li, Na, K) in SA-CVD are first clarified. Based on the current development
in SA-CVD growth and its related reaction modes, the existing methods are cate-
gorized into the Salt 1.0 (halide salts-based) and Salt 2.0 (molten salts-based)
techniques. The achievements, advantages, and limitations of each technique
are discussed in detail. Finally, new perspectives are proposed for the application
of SA-CVD in the synthesis of 2D transition metal dichalcogenides for advanced
electronics.
INTRODUCTION
The rapid growth of technology in recent years, coupled with the emergence of artificial intelligence, the
Internet of Things, and big data analytics, has led to an extremely high demand for processors with high
calculation capability and speed. The traditional three-dimensional (3D) silicon semiconductor
manufacturing technique is fast approaching the physical and process limits at a technology node of
2 nm. This will hinder the further development of current silicon semiconductor manufacturing techniques
and prevent further scaling down. Therefore, new materials with a characteristic size of nanometer or sub-
nanometer levels must be explored for application in future electronics. Atomically thin two-dimensional
(2D) layered materials that demonstrate superior electrical properties could supplement 3D silicon semi-
conductor techniques and extend Moore’s law to an ultimate technology node limit of 1 nm (Liu et al.,
2021; Su et al. 2021).
The mechanical exfoliation of bulk graphite to form atomically thin graphene using scotch tape unlocked
the potentials of 2D materials (Novoselov et al., 2004). New physics and applications have been developed,
and even 2D transition metal dichalcogenides (TMDCs), a large family of layered compounds beyond gra-
phene, have also been prepared using the same method (Novoselov et al., 2005). Among these exfoliated
2D TMDCs, monolayer MoS2-based field effect transistors (FETs), with a record high electron mobility of
200 cm2/Vs and a high current on/off ratio of 108 at room temperature, have stimulated significant
research interest to study many other 2D TMDCs (Radisavljevic et al., 2011).
Although mechanical exfoliation can be used to prepare high-quality 2D materials, it cannot be used to
fabricate large-area 2D materials with high yield and reproducibility. Therefore, an alternative fabrication
method must be developed to synthesize 2D materials for practical applications in future electronics and
optoelectronics. Chemical vapor deposition (CVD) has been widely used to fabricate one-dimensional (1D)
nanowires and nanotubes since the 1990s, as it offers good controllability, high yield at low cost. Therefore,
it could provide a practical solution to fabricate large-area, uniform, and high-quality 2D materials for
1International Center for
future applications. Young Scientists (ICYS),
National Institute for
Salt-assisted (SA)-CVD growth of 2D materials using halide salts and molten salts has been intensively stud- Materials Science (NIMS),
Tsukuba 305-0044, Japan
ied in recent years. In this review, the pioneering studies on the SA-CVD growth of 2D TMDCs will first be
*Correspondence:
introduced, followed by clarifying the unique roles of halogens and alkali metals played in the reaction. li.shisheng@nims.go.jp
Based on the growth mechanisms, current SA-CVD growth is categorized into two major techniques— https://doi.org/10.1016/j.isci.
the Salt 1.0 (halide salts-based) and Salt 2.0 (molten salts-based). Next, the applications, advantages 2021.103229
iScience 24, 103229, November 19, 2021 ª 2021 The Author(s). 1

This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
ll iScience
OPEN ACCESS Review
and limitations of each technique are reviewed systematically. Finally, the potential and challenges of using
SA-CVD to fabricate 2D TMDCs for future electronics are discussed.
Growth mechanism of halide salt-assisted CVD (HSA-CVD) of 2D TMDCs

Conventional CVD
The conventional CVD setup used to grow 2D TMDCs (e.g., MoS2) is illustrated in Figure 1A. In a CVD pro-
cess, a crucible containing a transition metal oxide (TMO) powder and growth substrates are loaded in the
high-temperature center, and chalcogen powder is loaded upstream in the low-temperature region. CVD-
grown MoS2 was first demonstrated in 2012 by the decomposition of (NH4)2MoS4, and the sulfurization of a
Mo film and MoO3, respectively (Lee et al., 2012; Liu et al., 2012; Zhan et al., 2012). Compared to the decom-
position of (NH4)2MoS4 (which releases H2S when preparing an aqueous solution) and the deposited Mo
film, stable MoO3 powder offers significant feasibility for growing large MoS2 monolayers with good
optical and electrical qualities (Figure 1B). The growth of MoS2 monolayers follows the typical vapor–
solid–solid (VSS) mode. First, sulfur and MoO3 powders are vaporized at sufficiently high temperatures.
Second, inert carrier gas is used to transport the sulfur and MoO3 vapors onto the solid growth substrates
to initiate the chemical reaction (Table 1a), which leads to the nucleation and growth of solid MoS2 mono-
layers. Later, this simple CVD growth technique using TMOs has become the dominant method not only for
fabricating MoS2 (Ji et al., 2013; Najmaei et al., 2013), but also for growing large variety of 2D TMDC mono-
layers. However, CVD presents several challenges when growing some 2D materials. For example, more
critical growth conditions are required to grow WSe2 monolayers (Figures 1C and 1D) (Huang et al.,
2014). To generate a sufficiently large volume of WO3 vapor and initiate the chemical reaction shown in Ta-
ble 1b, a high temperature of >925 C and a low pressure of 1 Torr are required to vaporize the high-
melting-point WO3 (Tm = 1473 C), which is significantly higher than that of MoO3 (Tm = 795 C).
Role of halogens in HSA-CVD

To enable the CVD growth of 2D TMDCs in mild conditions, the growth of large WSe2 and WS2 monolayers
was first demonstrated via the use of alkali metal halides as growth promoters in 2015 (Figures 1E–1G) (Li
et al., 2015b). By mixing tungsten oxides (WO2.9, 1473 C) with halide salts (AX, A = Na, K; X = Cl, Br, I), WSe2
and WS2 monolayers can be grown at atmospheric pressure and significantly lower temperature of 700 C,
which is more than 100 C lower than the same process using only tungsten oxide. The as-grown WSe2 and
WS2 monolayers are free of Na contamination after rinsing in IPA/H2O solution, and show high carrier mo-
bilities and high current on/off ratios when used as channel materials in field-effect transistors (FETs). The
enhanced CVD growth of tungsten-based 2D TMDCs can be attributed to the formation of tungsten oxy-
halides through reactions between tungsten oxide and halide salts at temperatures above 600 C (Table 1c).
The in-situ generated tungsten oxyhalides have melting points of less than 300 C and their high vapor pres-
sure makes them good precursors for growing high-quality WSe2 and WS2 monolayers in mild conditions.
This mechanism is the same as the Br2 and I2 used in the chemical vapor transport (CVT) growth of bulk crys-
tals, wherein the halogens facilitate the vaporization and transportation of metal precursors from the hot
end to the cool end of a sealed quartz tube via the formation of volatile intermediates (Schmidt et al., 2013).
Ahead of this study, Kang et al. also reported the 4-inch wafer-scale growth of monolayer MoS2 and WS2
films using a metal organic (MO)-CVD system (Kang et al., 2015). They attributed the enhanced growth to
the use of NaCl, KCl, and NaBr as desiccants. However, Kim et al. failed to observe enhanced growth of
MoS2 monolayers when more effective desiccants such as CaCl2 and CaO are employed (Kim et al.,
2017). Instead, they achieved the 4-inch wafer-scale growth of uniform MoS2 and WS2 monolayers with a
large grain size of up to several tens to hundreds of micrometers through the direct spin-coating of
NaCl and KI aqueous solutions onto growth substrates (sapphire). In general, the grain size of as-grown
MoS2 and WS2 films is about 1–2 orders of magnitude larger when halide salts are employed.
Role of alkali metals in HSA-CVD

Alkali metals (Li, Na, K) are important components of alkali metal halide salts which behave completely
different from the halogens in the SA-CVD growth of 2D TMDCs. Their role of liquefying/stabilizing
TMOs was first depicted in the vapor–liquid–solid (VLS) growth of 1D monolayer MoS2 nanoribbons in
2018 (Li et al., 2018). This process is illustrated in detail in Figure 1H. First, NaCl reacts with MoO3 to
form a molten salt—Na2Mo2O7 (Tm = 605 C). As its melting point is below the growth temperature of
700 C and it has poor wettability on the surfaces of NaCl and MoS2, the molten Na2Mo2O7 tends to
2 iScience 24, 103229, November 19, 2021

iScience ll
Review OPEN ACCESS
Figure 1. Mechanism of HSA-CVD growth of 2D TMDCs

(A and B) (A) Schematic illustration and (B) optical images of CVD-grown MoS2 monolayers through sulfurization of MoO3 powder. Reprinted with permission
from Lee et al. (2012). Copyright 2012, John Wiley & Sons, Inc.
(C and D) (C) Schematic illustration and (D) optical image of CVD-grown WSe2 monolayers through selenization of WO3 powder. Reprinted with permission
from Huang et al. (2014). Copyright 2014, American Chemical Society.
(E) Schematic illustration and conditions for SA-CVD growth of 2D WSe2 and WS2 monolayers.
(F and G) Optical images of (F) WSe2 and (G) WS2 monolayers fabricated through SA-CVD. Reprinted with permission from Li et al. (2015b). Copyright 2015,
Elsevier.
(H) Schematic illustration of SA-CVD growth of 1D MoS2 nanoribbons. Reprinted with permission from Li et al. (2018). Copyright 2018, Nature Publishing
Group.
(I) Schematic illustration of the roles of the halogen and alkali metal in SA-CVD growth of 2D TMDCs. Halogens react with metal oxides to form metal
oxyhalides, which facilitate the growth of 2D materials through vapor–solid–solid (VSS) mode. Alkali metals liquefy and stabilize metal oxides to form molten
salts, escalating growth via vapor–liquid–solid (VLS) mode.
(J) Real time observation of the SA-CVD growth of WSe2.
(K) Raman spectrum of the solidified intermediate compound, wherein the peaks marked with dashed red lines correspond to the Raman modes of Na2WO4.
Reprinted with permission from Rasouli et al. (2019). Copyright 2019, Royal Society of Chemistry.
form hemispherical droplets on the surfaces. After saturation with sulfur vapor, solid MoS2 monolayers are
precipitated from the Na-Mo-O-S droplets (Table 1d). Besides the dominant 1D VLS growth, VSS growth
also occurs owing to the presence of volatile molybdenum oxychlorides (MoOuClv), which widens the
iScience 24, 103229, November 19, 2021 3

ll iScience
OPEN ACCESS Review
Table 1. Possible reactions in CVD growth of 2D TMDCs
Reactions References
a. MoS2 MoO3(g) + S(g) / MoS2(s) + SO2(g) Lee et al. (2012)
b. WSe2 WO3(g) + Se(g) + H2(g) / WSe2(s) + SeO2(g) + H2O(g) Huang et al. (2014)
c. WSe2, WS2 WO2.9(s) + NaCl(s) / NaWO3(s) + WOCl4(g) + WO2Cl2(g) + WO2(s) + W(s) Li et al. (2015b)
WOCl4(g) + WO2Cl2(g) + Se(g) + H2(g) / WSe2(s) + HCl(g) + H2O(g)
d. MoS2 3MoO3(s) + 2NaCl(s) / Na2Mo2O7(l) + MoO2Cl2(g) Li et al. (2018)
Na2Mo2O7(l) + 7S(g) / 2MoS2(s) + Na2SO3(s) + 2SO2(g)
e. WSe2 2WO3(s) + 2NaCl(s) / WO2Cl2(g) + Na2WO4(l) Rasouli et al. (2019)
Na2WO4(l) + 2H2Se(g) + H2(g) / WSe2(s) + 3H2O(g) + Na2O(s)
WO2Cl2(ads) + 2H2Se(ads) + H2(g) / WSe2(s) + 2H2O(g) + 2HCl(g)
f. TiS2 NH4Cl(s) / NH3(g) + HCl(g) Gao et al. (2018)
2Ti(s) + 2xHCl(g) / 2TiClx(g) + xH2(g)
2TiClx(g) + xH2(g) + 4S(g) / 2TiS2(s) + 2xHCl(g)
g. NbxW1-xS2 NaCl(s) + NbCl5(s) / NaNbCl6(s) Jin et al. (2019)
WO3(s) + NaCl(s) / NaWO3(s) + WOCl4(g) + WO2Cl2(g)
NaNbCl6(s) + S(g) + WOCl4(g) + WO2Cl2(g) + H2(g) /
NbxW1-xS2(s) + HCl(g) + H2O(g) + H2S(g)
h. SnxMo1-xS2 SnO2(s) + NaCl(s) / SnOyClz(g) + ... Mo et al. (2019)
SnOyClz(g) + MoO3(g) + S(g) / Mo1-xSnxS2(s) ...
i. MoSe2 2(NH4)2MoO4(s) / 2MoO3(s) + 4NH3(g) + 2H2O(g) Kim et al. (2021)
2MoO3(s) + 2KI(s) / MoO2I2(g) + K2MoO4(l)
MoO2I2(g) + 4H2(g) + 3Se(g) / MoSe2(s) + 2HI(g) + 2H2O(g) + H2Se(g)
j. MoS2 Mo(s) + NaCl(s) + O2(g) / Na2MoO4(s) + MoOCl4(g) Yang et al. (2019b)
MoS2 nanoribbons (lateral growth). Consequently, contrasts of the inner and outer regions of the wide
MoS2 nanoribbons can be observed in the scanning electron microscope (SEM) and transmission electron
microscope (TEM) images. To rule out the effects of chalcogens, the VLS growth of Mo- and W-based 2D
TMDCs was confirmed through the simple sulfurization, selenization, and tellurization of molten salts—
Na2MoO4 and Na2WO4, respectively (Li et al., 2018).
Definition of Salt 1.0 and Salt 2.0 growth techniques

Based on the research on the HSA-CVD growth of 2D TMDCs, including the VSS growth of 2D WSe2 and WS2
monolayers and the VLS growth of 1D MoS2 nanoribbons, the roles of halogens and alkali metals can be gener-
alized as shown in Figure 1I. Considering NaCl—this is also applicable to other alkali metal halide salts—the
halogen, Cl reacts with TMOs to form highly volatile metal oxychlorides (MOuClv) with low-melting points
(<300 C). The vapors of these metal oxychlorides can travel long distances to the growth substrates and initiate
the VSS growth of 2D TMDCs. In contrast, Na reacts with TMOs to form non-volatile molten salts (NaxMOy) with
high melting points (>600 C) directly on the growth substrates without vapor phase transportation. After reac-
tion with chalcogen vapor, solid 2D TMDCs are grown from the liquid melts in the VLS mode. The coexistence
of the VSS and VLS modes because of the in-situ generated WO2Cl2 and Na2WO4 was also verified through the
real-time optical observation of the NaCl-assisted CVD growth of WSe2 (Figures 1J and 1K, Table 1e) (Rasouli
et al., 2019). Despite the coexistence of volatile metal oxyhalides and molten salts in the HSA-CVD growth of 2D
TMDCs, the former plays the dominant role as effective precursors in most studies. Consequently, it is improper
to refer to halide salts as molten salts, as this may lead to a misunderstanding regarding the growth mechanism.
Based on the above-mentioned growth mechanism and development of SA-CVD, it can be categorized
into two growth techniques. The Salt 1.0 technique uses halide salts (AX, X = F, Cl, Br, I) as growth
promoters/precursors and consists of a dominant VSS mode and an indispensable VLS mode when A rep-
resents alkali metals. The Salt 2.0 technique uses molten salts (e.g., Na2MoO4, Na2WO4, etc.) as growth
precursors and only involves a VLS mode.
It is worth mentioning that the complex growth mechanism including the thermodynamics and kinetic pro-
cesses in SA-CVD growth of 2D TMDCs must be studied further. Especially, how halogens and alkali metals

iScience ll
Review OPEN ACCESS
involved in the nucleation and growth of 2D TMDCs are still elusive. Although the exact chemical reactions
are difficult to describe, the possible reactions proposed in related literature can be used to better under-
stand the growth mechanism of SA-CVD (Table 1).
Applications of HSA-CVD (Salt 1.0 technique)

Compared to the conventional CVD using TMO powders only, HSA-CVD has impressive potential for
growing 2D materials under mild conditions, with better controllability, improved yield, and reproduc-
ibility. In this section, the main achievements of HSA-CVD will be discussed in the following aspects: (1)
versatility; (2) doping; (3) phase; and (4) heterostructure.
Versatility in growing 2D materials

The most impressive achievement of HSA-CVD is that it can be utilized to grow 47 different types of 2D
materials including 32 binary metal chalcogenides (Figure 2A), MX2 and MX (M = Mo, W, Re, Ti, Zr,
Hf, V, Nb, Ta, Pt, Pd, Fe; X = S, Se, Te), 13 ternary and quaternary alloys, and 2 heterojunctions (Zhou
et al., 2018). Pure metals, such as Ta and Re, have also been directly mixed with NaCl or KI to grow Ta-
and Re-based 2D TMDCs. The use of mixed metal–halide salt precursors provides a more reliable strategy
instead of using their non-stable, highly volatile, toxic halides. For instance, Gao et al. grew semi-metallic
TiS2 using mixed Ti–NH4Cl instead of titanium chlorides (Table 1f) (Gao et al., 2018).
Owing to its versatility, feasibility, and reproducibility, the HSA-CVD method (Salt 1.0 technique) has even
been used to grow sensitive 2D TMDCs without using molecular beam epitaxy under vacuum conditions.
Wang et al. reported on the simple CVD growth of high-quality 2D superconducting NbSe2 monolayers
using NbOx-NaCl and charge density wave conductor–TiSe2 using TiOx-LiCl, respectively (Wang et al.,
2017a, 2018). The advantage of using partially oxidized metal powders (e.g., NbOx, TiOx) is that the release
rate and amount of in-situ generated metal oxychlorides can be controlled effectively. Besides 2D layered
crystals, Hu et al. reported on the halide salt-induced self-limited growth of ultrathin Ge flakes using a GeS-
KCl mixture (Hu et al., 2018). As shown in Figure 2B, the successful growth of non-layered Ge flakes can be
primarily attributed to preferential growth of the lowest formation energy (111) plane and the giant inter-
face distortion caused by the Cl-Ge motif.
Beside the widely used metal chlorides, bromides and iodides, metal fluorides were also employed for
enhanced CVD growth of 2D materials until very recently. In 2019, Liu et al. demonstrated fast and
enhanced CVD growth of graphene on copper foils that were placed on fluoride substrates (Figure 2C)
(Liu et al., 2019). This was an important addition to the research on HSA-CVD as it confirmed the inclusion
of fluorides (MF2, M = Mg, Ca, Ba) as effective growth promoters. Large graphene films with a lateral size of
1 mm can be grown at a fast rate of 200 mm/s (Figure 2D). The rapid growth can be attributed to the
released F2, which lowers the dissociation energy of CH4 to a more active carbon species. Fluorides also
promote the growth of h-BN, WS2, and MoSe2. Therefore, HSA-CVD is a versatile fabrication method,
not only for 2D metal chalcogenides, but also for graphene and h-BN.
Later, Chang et al. deposited trilayer NaF–SiO2–MoO3 films on sapphire substrates to realize the fast
growth of large monolayer and bilayer MoS2 (1.1 mm/200 mm) in 10 min, and fabricated fully covered films
on centimeter-scale substrates that had a record-high average grain size of 450 mm (Chang et al., 2020). As
illustrated in Figure 2E, MoO3 can diffuse through the cracks in the thin SiO2 layer and initiate the reaction
between NaF and MoO3 to generate molten Na2Mo2O7 and volatile MoO2F2 vapor. The molten Na2Mo2O7
can keep diffusing on the surface of the NaF layer and grow into large droplets with a prolonged reaction
time. Therefore, the growth of monolayer, bilayer, and even trilayer MoS2 can be achieved by initializing the
sulfurization of Na2Mo2O7 droplets at different growth stages.
Doping
Doping heteroatoms into host materials can effectively modify their crystal and electronic structures, and
significantly improve their electrical, optical, magnetic, and catalytic properties. In recent years, a signifi-
cant amount of research has been conducted on the CVD growth of doped 2D TMDCs. However, if the
melting points and vapor pressures of the host and dopant metal precursors differ significantly, it is
hard to simultaneously vaporize both metal precursors during the CVD process. While HSA-CVD plays
an important role in growing doped 2D TMDCs. For instance, Nb-doped WS2 monolayers were grown us-
ing a mixed WO3–Nb–NaCl precursor; atomic resolution STEM revealed that the substitutional doping of

ll iScience
OPEN ACCESS Review
Figure 2. Applications of HSA-CVD (Salt 1.0 technique)

(A) Library of atomically thin metal chalcogenides grown using HSA-CVD. Reprinted with permission from Zhou et al. (2018). Copyright 2018, Nature
Publishing Group.
(B) Halide-induced self-limited growth of non-layered Ge thin flakes using GeS-KCl as precursors. Reprinted with permission from Hu et al. (2018). Copyright
2018, American Chemical Society.
(C) Schematic illustration of fluoride-assisted CVD growth of graphene.
(D) SEM image of 1 mm graphene grown on copper foil in 5 s. Reprinted with permission from Liu et al. (2019). Copyright 2019, Nature Publishing Group.
(E) Schematic illustration and optical images of the rapid CVD-grown large, layer-number tunable MoS2 using a self-capping VLS method. Reprinted with
permission from Chang et al. (2020). Copyright 2020, Nature Publishing Group.
(F) Schematic illustration of the growth of Nb-doped WS2 monolayers using WO3–Nb-NaCl as a precursor.
(G) Atomic-resolution STEM image of the substitutional doping of Nb at W site. Reprinted with permission from Sasaki et al. (2016). Copyright 2016, The
Japan Society of Applied Physics.
(H) Vapor pressure evolution of TM precursors for the sequential growth of MoS2 and SnxMo1-xS2 using separated MoO3–NaCl and SnO2–NaCl.
(I) AFM image of the as-grown MoS2–SnxMo1-xS2 in-plane heterojunction. Reprinted with permission from Shao et al. (2020). Copyright 2020, The Authors.
(J) Phase controlled growth of 2H-1T’ MoTe2 in-plane junctions using MoO3–NaCl. Reprinted with permission from Sung et al. (2017). Copyright 2017, Nature
Publishing Group.
(K) Optical image of vertical NbS2–MoS2 heterojunction through one-step sulfurization of the separated MoO3 and Nb2O5–NaCl. Reprinted with permission
from Fu et al. (2018b). Copyright 2018, American Chemical Society.

iScience ll
Review OPEN ACCESS
Nb occurred at the W sites in the WS2 monolayers (Figures 2F and 2G) (Sasaki et al., 2016). With small Nb
dopants (0.5 atom%), new broad photoluminescence (PL) emissions occurred at 1.4–1.6 eV in addition to
the PL emission of WS2 monolayers at 1.98 eV. Mixed WO3–NbCl5–NaCl has also been used to grow
Nb-doped WS2 monolayers (Table 1g) (Jin et al., 2019; Tang et al., 2021). Compared to Nb, NbCl5 has a
higher doping ability owing to its lower melting point and higher vapor pressure. Similarly, Eu-doped
MoS2 (Eu2O3–NaCl) (Xu et al., 2018), V-doped MoS2 (Mo6V9O40–NaCl) (Zhang et al., 2020), Fe/Co/Mn-
doped MoS2 (MoO3 + Fe3O4/CoO/MnOx–NaCl) (Cai et al., 2020; Li et al., 2020b), and Sn-doped MoS2
(MoO3 + SnO2–NaCl) (Table 1h) (Mo et al., 2019) have also been successfully grown using NaCl as a growth
promoter. In principle, the doping concentration can be tuned by varying the ratio of the metal precursors.
However, in reality, it is quite challenging to simultaneously vaporize the metal precursors at a fixed rate
and guarantee the uniform spatial distribution of the metal precursor vapors. Consequently, it is difficult
to grow uniformly doped 2D TMDCs with the desired doping concentration and properties. Nevertheless,
Shao et al. exploited the sequential vaporization of metal precursors to grow lateral MoS2–SnxMo1-xS2 in-
plane heterojunctions using separated MoO3–NaCl and SnO2–NaCl as precursors (Shao et al., 2020). As the
melting point of MoO3 (Tm = 795 C) is much lower than that of SnO2 (Tm = 1630 C), the in-situ generated
MoOuClv vapor initiated the growth of the inner MoS2 layer first, and the later generated SnOmCln and
MoOuClv vapors result in the growth of outer SnxMo1-xS2 layer (Figures 2H and 2I).
Phase
The phase of 2D TMDCs represents their polymorphism. Based on their atomic structures, monolayer 2D
TMDCs have mainly 1H, 1T, and 1T0 phases. These phases provide various electrical, optical, and catalytic
properties to 2D TMDCs. For instance, semiconducting 1H-TMDCs are primarily used as channel materials
in FETs or optoelectronic devices (Wang et al., 2012), whereas metallic 1T0 -TMDCs can be used as high-per-
formance contacts in TMDC-based FETs (Kappera et al., 2014) and catalytic electrodes for hydrogen evo-
lution (Voiry et al., 2013). Consequently, phase conversion and phase-controlled synthesis of metastable
1T0 -TMDCs have received significant attention in recent years (Lai et al., 2021; Liu et al., 2018; Voiry
et al., 2015; Yu et al., 2018). HSA-CVD has been widely used to grow phase-controlled 2D TMDCs. For
instance, 1T0 -MoTe2 was grown through the tellurization of MoO2–KI (Zhang et al., 2017b). Coplanar semi-
conducting-metallic 2H-1T0 MoTe2 in-plane junctions were grown using MoO3–NaCl by varying the growth
temperatures (Figure 2J) (Sung et al., 2017). This unique CVD-grown heterojunction was able to provide a
reduced Schottky barrier and improved electrical contacts in 2H-1T0 MoTe2-based FETs. Similarly, phase-
selective 1H- and 1T0 -MoS2 and their heterojunctions have been grown by the sulfurization of MoO2–KCl
and the decomposition of K2MoS4, respectively (Arreola et al., 2021; Liu et al., 2018). In these studies,
the strong electron doping effect of alkali metals play vital important role. Only the surface adsorbed alkali
metals to some extent, the formation energy of 1T0 phase was smaller than that of 1H phase. Furthermore,
Shao et al. reported that KX (X = Cl, Br, I) is preferable for growing 1T-SnS2, whereas NaX is more suitable
for growing 2H-SnS2 (Shao et al., 2019). Therefore, the alkali metal halide salts and growth conditions (e.g.,
temperatures, H2 concentration, etc.) must be carefully chosen and tuned to achieve phase-selective
growth of 2D TMDCs.
Heterojunctions
Heterostructures (in-plane and vertical) can be assembled using two or more 2D TMDCs to introduce new
properties compared to individual components (Tan et al., 2021). Based on the electrical properties of 2D
TMDCs—metals (M) and semiconductors (S), two main M–S and S–S heterojunctions are intensively stud-
ied. M–S junctions are primarily grown for contact engineering of 2D TMDC-based FETs (Li et al., 2020a),
whereas S–S type TMDC-based PN junctions have significant potential for application in solar cells, pho-
todetectors, and light emission devices (Furchi et al., 2014; Lee et al., 2014; Li et al., 2015a). However, it
is difficult to grow high-quality TMDC-based heterojunctions with arbitrary combinations. During the
sequential growth of different 2D TMDCs at high temperatures (>600 C), severe degradation is inevitable,
especially for heterojunctions with different chalcogens. This is primarily because the stability of different
2D TMDCs varies (sulfides > selenides > tellurides). Nevertheless, HSA-CVD has been employed to lower
the growth temperature and maintain the grown 2D TMDCs intact. As shown in Figure 2K, vertical MoS2–
NbS2 junctions were achieved through one-step sulfurization of separated MoO3 and Nb2O5–NaCl (Fu
et al., 2018b). Similarly, WS2–NbS2 in-plane junctions were obtained through the sequential growth of
WS2 and NbS2 using WO3 and Nb2O5–NaCl (Zhang et al., 2018). MoS2–WS2 in-plane junctions were also
grown via NaCl-assisted simultaneal sulfurization of separated MoO2 and WO3 powders (Wang et al.,
2017b). The above-mentioned heterojunctions are still poor in controlling the geometric configuration

ll iScience
OPEN ACCESS Review
Figure 3. Evolution of HSA-CVD

(A) Poor batch-to-batch reproducibility in the CVD growth of MoS2 through the sulfurization of MoO3 powder.
(B) Optical images of as-grown MoS2 on SiO2/Si with inevitable byproduct contamination. Reprinted with permission from Li et al. (2019). Copyright 2019,
Royal Society of Chemistry.
(C) Schematic illustration of the growth of wafer-scale MoS2 using (NH4)2MoO4–NaCl-coated silica gel plate. Reprinted with permission from Wang et al.
(2020). Copyright 2020, American Chemical Society.
(D and E) (D) Schematic illustration of depositing (NH4)2MoO4–KI liquid precursor to grow (E) a large-area monolayer MoSe2 film. Reprinted with permission
from Kim et al. (2021). Copyright 2021, American Chemical Society.
(F) Schematic illustration of the liquid precursor for growing monolayer V-doped WSe2 flakes. Reprinted with permission from Fan et al. (2020). Copyright
2019, The Authors.
and components. To satisfy their application in electronics, more efforts should be devoted to developing
low-temperature growth techniques for high-quality 2D TMDC-based heterojunctions.
Upgrading of HSA-CVD (Salt 1.0 + technique)

Despite its numerous advantages, HSA-CVD (Salt 1.0 technique) also has multiple drawbacks. One severe
issue is the excessive and non-uniform vapors of the transition metal (TM) precursors in the growth cham-
ber, because of which the growth of 2D TMDCs strongly relies on the position of the substrates. Figure 3A
shows the different deposition patterns on growth substrates in three different batches (Li et al., 2019). In
addition to the desired 2D TMDC monolayers, inevitable byproducts such as TMOs and thick 2D TMDCs
were also deposited on the growth substrates, severely hindering the application of CVD-grown 2D
TMDCs (Figure 3B). Moreover, these byproducts can contaminate the crucibles and growth chambers,
which must be cleaned or replaced frequently, thereby increasing the production cost. To overcome
these detrimental effects of TMO powders, alternative soluble TM precursors in aqueous solutions
can be employed to minimize their use in SA-CVD. For example, large-area monolayer and few-
layer 1T0 -MoTe2 (1 mm) and 1T0 -WTe2 (350 mm) were grown using (NH4)6Mo7O24–KCl and
(NH4)10W12O41–KCl aqueous solutions (Chen et al., 2017b). Phase-selective 2H- and 1T0 -MoTe2 were
grown using soluble (NH4)6Mo7O24–NaCl as a precursor by modulating the growth temperature (Hoang
et al., 2018). Two-inch wafer-scale pristine and Re-doped MoS2 monolayers were grown using soluble
(NH4)2MoO4–NaCl as a host precursor and solid ReCl3 powder as the dopant precursor (Figure 3C)
(Wang et al., 2020). Dirac semi-metallic PtTe2 flakes with ultrahigh conductivity were epitaxially grown
on mica using soluble PtCl4–NaCl (Fu et al., 2018a). Unlike the direct load of a large amount of mixed
TMO-halide salt powders in crucibles, the mixed TM precursor-halide salt can be deposited more uni-
formly by drop-casting their aqueous solutions into crucibles or onto a silica gel plate. Therefore, these
crucibles/silica gels can release TM precursors more uniformly in the typical CVD process, resulting in
more uniform 2D TMDCs with high growth reproducibility. However, the crucibles/silica gels still undergo
contamination, making it difficult to clean and reuse them.

iScience ll
Review OPEN ACCESS
Alternatively, the aqueous solutions of mixed precursors, such as (NH4)2MoO4–KI, (NH4)2WO4–KI, and
(NH4)6Mo7O24–NaCl, were directly spin-coated on growth substrates to grow wafer-scale 2D TMDCs (Fig-
ures 3D and 3E) (Kim et al., 2021; Zhang et al., 2021a). However, these ammonia molybdates/tungstates
have poor thermal stability and provide a low yield of 2D TMDCs. During the CVD process, the ammonia
molybdates/tungstates first decompose to form MoO3/WO3 and release NH3 at temperatures of above
100 C. Only when mixed with a proper amount of alkali metal halide salts, large-area continuous TMDC
films can be grown successfully. Although these studies attribute this high-efficiency growth to the forma-
tion of volatile TM oxyhalides (Table 1i), the contribution of the alkali metals that can liquefy and stabilize
TMOs during the HSA-CVD process should not be ignored. The importance of alkali metals is further veri-
fied by pre-deposition of sodium cholate (without halogens) on growth substrates to promote the growth
of MoS2, 1T0 -MoTe2, and 1T0 -WTe2 (Han et al., 2015; Naylor et al., 2016, 2017) using (NH4)6Mo7O24 and
(NH4)6H2W12O40 aqueous solutions, respectively. Similarly, NaOH can also be mixed with (NH4)6H2W12O40
and NH4VO3/C4H4NNbO9 in aqueous solutions to enhance the growth of V/Nb-doped WSe2 (Figure 3F)
(Fan et al., 2020; Vu et al., 2021; Yun et al., 2020). Therefore, alkali metals play a more significant role
than halogens in stabilizing the soluble TM precursors on growth substrates and enhancing the growth
of 2D TMDCs. In addition, the in-situ generated volatile TM oxyhalides have minimal impact to the growth
environments due to limited loading amount of soluble TM precursors on growth substrates.
Applications of molten salt-CVD (Salt 2.0 technique)

In contrast to the Salt 1.0 technique with its complex VSS and VLS growth modes, the Salt 2.0 technique uses
molten salts to grow 2D TMDCs in the VLS mode. To guarantee the success of the Salt 2.0 technique, the
molten salts must meet three main criteria (Figure 4A): (1) reasonably high melting points; (2) ability to form
stable melts with a low vapor pressure at CVD growth temperatures; and (3) soluble in H2O. The first two criteria
ensure the VLS growth of 2D TMDCs, whereas the third criterion can ensure the deposition of molten salts
through easy methods such as spin coating, drop casting, ink-jet printing, and so forth. Fortunately, a large
group of molten salts with a chemical formula of AxMOy (A-alkali metals; M-transition metals) can be used
as precursors to grow 2D TMDCs. Some of these, such as Na2MoO4 and Na2WO4, have been proved to be
ideal precursors, and have been widely used to grow Mo- and W-based 2D TMDCs (Cun et al., 2019; Li
et al., 2018; Ma et al., 2021). Spin coating of their aqueous solutions is the most used method to deposit molten
salts on growth substrates (Figure 4B). To guarantee the uniform deposition of molten salts, the surface of
growth substrates must be hydrophilic. Therefore, UV-O3, oxygen plasma and piranha solution can be utilized
to treat the growth substrates. In addition, by varying the concentration of the molten salt solutions and the
spin-coating rate, the amount of deposited molten salt can be varied. Consequently, the surface coverage,
domain size, and layer numbers of the TMDC flakes/films can be engineered. Recently, 2-inch wafer-scale
monolayer MoS2 and WS2 films were successfully grown with spin-coated Na2MoO4 and Na2WO4 aqueous so-
lutions on sapphire and SiO2/Si substrates, respectively (Figures 4C–4F) (Li et al., 2019; Liu et al., 2020). Consid-
ering the CVD growth of 2D MoS2 monolayers using the Salt 2.0 technique, spin-coated Na2MoO4 particles are
first melted by heating them up to the growth temperature, 750 C, which is above its melting point. Owing to
the low vapor pressure of Na2MoO4 (Kazenas et al., 2010), stable Na2MoO4 melts have good wettability on
Al2O3 and SiO2/Si substrates are formed (Figure 4C). After adsorbing sulfur vapor, solid MoS2 monolayers
are precipitated from the sulfur-saturated Na-Mo-O-S melts as illustrated in Figure 1I. Furthermore, monolayer
MoS2 arrays can be successfully grown using patterned Na2MoO4, which cannot be achieved with volatile
MoOuClv and MoO3 without using pre-deposited nucleation seeds.
Although the Salt 2.0 technique is well-suited to growing wafer-scale monolayer MoS2 and WS2 films, it is still
difficult to grow large-area transition metal selenides and tellurides. Recently, a mixed transition metal salt and
chalcogen salt, Na2MoO4–Na2SeO3 was developed to achieve a wafer-scale growth of monolayer MoSe2 film
with a grain size of 100–250 mm and unprecedented uniformity (Figure 4G) (Li et al., 2021b). The enhanced
growth of MoSe2 can be attributed to the direct formation of intermediate Na-Mo-O-Se melts from the mixed
Na2MoO4–Na2SeO3. Compared to Na–Mo–O melts, the Na–Mo–O–Se melts are a step closer to the final
MoSe2 monolayers, and consequently, it kinetically favors the nucleation and growth of MoSe2 monolayers.
It is also applicable for the enhanced growth of 2D ReSe2 and WTe2 using mixed NaReO4–Na2SeO3 and
Na2WO4–Na2TeO3, respectively. Therefore, using mixed molten transition metal and chalcogen salts is a ver-
satile option for growing large groups of 2D TMDCs and is an important upgrade to the Salt 2.0 technique.
Besides the growth of large-area wafer-scale binary 2D TMDCs, the Salt 2.0 technique also provides great
controllability for growing doped/alloyed 2D TMDCs using mixed salt aqueous solutions instead of powdered

ll iScience
OPEN ACCESS Review
Figure 4. Application of molten salt-CVD (Salt 2.0 technique)

(A) Three main criteria for Salt 2.0 technique.
(B) Schematic illustration of the deposition of molten salt onto a growth substrate through spin-coating of its aqueous solution.
(C) Schematic illustration of a wafer-scale and patterned growth monolayer MoS2 film using Na2MoO4 as a precursor.
(D and E) Optical images of (D) 2-inch monolayer MoS2 film and (E) patterned MoS2 array grown on sapphire substrates. Reprinted with permission from Li
et al. (2019). Copyright 2019, Royal Society of Chemistry.
(F) 2-inch wafer-scale monolayer WS2 film grown on SiO2/Si substrate using Na2WO4 as a precursor. Reprinted with permission from Liu et al. (2020).
Copyright 2020, American Chemical Society.
(G) Enhanced growth of 2-inch wafer-scale monolayer MoSe2 film using mixed Na2MoO4–Na2SeO3 as precursor. Reprinted with permission from Li et al.
(2021b).
(H) Schematic illustration of Re- and V-doped 2D TMDCs grown using mixed molten salts with tunable compositions. Reprinted with permission from Li et al.
(2021a). Copyright 2021, John Wiley & Sons, Inc.
(I) An optical image of a MoS2–WS2 vertical heterojunction grown with separated Na2MoO4 and Na2WO4. Reprinted with permission from Bai et al. (2021).
Copyright 2021, The authors.
(J) Conformal growth 2D TMDCs in optic fiber for super-high nonlinearity. Reprinted with permission from Zuo et al. (2020). Copyright 2020, Nature
Publishing Group.
precursors. Recently, tunable doping of rhenium (Re) and vanadium (V) into 2D MoS2, WS2, and WSe2 mono-
layers was achieved using Na2MoO4 and Na2WO4 as the host salts, and NaReO4 and NaVO3 as the dopant
salts (Figure 4H) (Li et al., 2021a). The stable mixed molten salts provide high flexibility in tuning the doping
concentration across a wide range by varying the dopant salt concentration, which is quite challenging in a
typical VSS growth process. For instance, Zou et al. grew V-doped MoS2 films with a wide doping concentra-
tion of 0.3–11.3 atom% (Zou et al., 2021). This was achieved only through the use of vanadium precursors with
various doping abilities (V2O5 < NH4VO3 < VCl3). As Re and V are neighbors of Mo and W in the periodic table,
they act as electron donors and acceptors when substitutional doping at the Mo and W sites in 2D TMDCs,
respectively. Therefore, Re and V doping can effectively modify the carrier types and concentrations of 2D
TMDCs. The optical and electrical properties of Re- and V-doped 2D TMDCs can be precisely tuned by varying
the composition of the mixed salt precursors. In particular, heavily V-doped WS2 and WSe2 exhibit a significant
increase in electrical conductivity, up to 108 times, compared to the intrinsic samples. Therefore, they are ideal

iScience ll
Review OPEN ACCESS
van der Waals contacts for p-type 2D TMDC-based FETs. Similarly, Qin et al. grew Nb-doped WS2 monolayers
using a mixed Na2WO4–Nb(HC2O4)5 aqueous solution, and achieved a high Nb doping density of 1014 cm2
(Qin et al., 2019). These studies have demonstrated that the Salt 2.0 technique using mixed molten salts are not
only limited to TM salts, but can also employ chalcogen salts to provide an effective method of growing large
groups of doped/alloyed 2D TMDCs with multiple metal and chalcogen components in the form of
(MuM0 vM00 w .) (SxSeyTe1xy)2. Not limited to the doped/alloyed 2D TMDCs using mixed molten salts, Na2-
MoO4 and Na2WO4 deposited on separated substrates can even enable the single-step CVD growth of
MoS2–WS2 vertical heterojunctions (Figure 4I) (Bai et al., 2021). This further demonstrates the applications
of molten salts for diverse structures of 2D TMDCs.
One more advantage of using aqueous solution is the possible coating of molten salt on the surfaces with
arbitrary shape and even the inner chamber of an object. This can further extend the growth/integration of
2D TMDCs to many other functional devices. Recently, Zuo et al. reported on the conformal growth of 2D
TMDCs in the channels of optical fibers (Zuo et al., 2020). As shown in Figure 4J, a Na2MoO4 aqueous so-
lution was first filled in the inner channels of optical fiber and dried. After sulfurization of the molten salts
using low-pressure CVD, MoS2 monolayers were conformally grown inside the optical fibers. The coverage
of the MoS2 monolayers can be easily engineered by tuning the concentration of the Na2MoO4 aqueous
solution. This simple method can also be applied to grow MoSe2 and WS2 inside the optical fibers. With
this novel integration of 2D TMDCs and optical fibers, ultrahigh non-linear optical properties that are
several hundred times higher than those of TMDC monolayers on flat substates were achieved.
Overall, the Salt 2.0 technique using molten salts is still in its infancy stage. However, it has clearly demon-
strated its efficacy in growing large-area wafer-scale 2D TMDC polycrystalline film, patterns, alloys, and
heterojunctions. Furthermore, by using a minimal amount of molten salt, the Salt 2.0 technique can reduce
the burden on the growth chambers, and significantly reduce the likelihood of contamination.
Alkali metals—two sides of the same coin

Regardless of the technique used, alkali metals are the indispensable component that promotes lateral
growth of the 2D TMDCs. Numerous alkali metal-based chemicals such as NaOH, KOH, Na2SO4,
KH2PO4, Na2CO3, KNO3, CH3COONa, C6H5O7Na3, PTAS, EDTA-4Na, etc., can be employed to enhance
the CVD growth of 2D TMDCs (Ling et al., 2014, 2016; Song et al., 2017; Wang et al., 2019a; Yang et al.,
2019a). However, the alkali metals may on one hand contaminate the TMDCs grown, leading to inferior de-
vice performance, poor stability, and even failure of the electronic devices. Therefore, it is vital to maximize
the beneficial effects of alkali metals in facilitating growth, while minimizing their negative impacts on
downstream applications. To achieve this, (i) the detailed roles and chemical states of the alkali metals
in the CVD process, and (ii) their distribution on the 2D TMDCs and growth substrates must be understood.
With that, a comprehensive evaluation of the impacts of alkali metals on the as-grown 2D TMDCs can be
performed, and an alkali metal removal strategy can be developed.
When 2D TMDCs are grown using the HSA-CVD process (Salt 1.0 technique), halide salt particles are often
found at edges of the as-grown TMDCs. As shown in Figure 5A, NaBr nanoparticles accumulated at the
periphery of the as-grown MoS2 monolayers that were grown using MoO2-NaBr. Li et al. claimed that
NaBr enables the synthesis of MoS2 monolayers through a surfactant-mediated growth mechanism without
forming molten salts. The Na ions in NaBr chemically passivate the edges of the growing MoS2 monolayers,
relaxing the in-plane strain to suppress vertical growth and promote lateral growth (Li et al., 2020c). In
contrast, Huang et al. attributed the rapid, high-quality, and controllable growth of MoS2 monolayers to
a new vapor–liquid–adatom–solid (VLAS) growth mode (Huang et al., 2020), where catalytic KCl particles
synergistically capture MoOx and S vapors. Oversaturated adatoms subsequently diffuse along the edges
to resume the lateral growth of the MoS2 monolayers (Figure 5B).
Despite the different growth mechanisms proposed, the alkali metal ions distribute basically all over the
growth substrates and even underneath the as-grown 2D TMDCs due to the strong chemical affinity
with oxide substrates (Figure 5C) (Han et al., 2021; Li et al., 2020c; Zhang et al., 2018). Because of the pres-
ence of these alkali metal ions at the TMDC-substrate interface, 2D TMDCs grown using SA-CVD can be
wet transferred with or without the mediation of a coated polymer (e.g., PMMA, PC, etc.) film in de-ionized
(DI) H2O. Compared to the use of corrosive and toxic etchants, such as HF, NaOH, and KOH, DI H2O pro-
vides a fast damage-free transfer process for SA-CVD grown 2D TMDCs (Kojima et al., 2019; Zhang et al.,

ll iScience
OPEN ACCESS Review
Figure 5. Alkali metals in the CVD growth of 2D TMDCs

(A) SEM image of NaBr nanoparticles on the edges of a MoS2 monolayer. Reprinted with permission from Li et al. (2020c). Copyright 2020, American
Chemical Society.
(B) Schematic illustration of edge-attached KCl assisted growth of MoS2 monolayers through a vapor–liquid–adatom–solid (VLAS) mechanism. Reprinted
with permission from Huang et al. (2020). Copyright 2020, American Chemical Society.
(C) TIF-SIMS elemental mapping showing the distribution on SiO2/Si substrate after CVD growth. Reprinted with permission from Li et al. (2020c). Copyright
2020, American Chemical Society.
(D) XPS core-level spectra of Na 1s in as-grown MoS2 on sapphire (top) and transferred MoS2 on SiO2/Si substrates (bottom) through NaCl-assisted MOCVD.
Reprinted with permission from Kim et al. (2017). Copyright 2017, American Chemical Society.
(E) Schematic illustration and image of 6-inch monolayer MoS2 film grown on glass substrate.
(F and G) DFT-calculated energy diagrams for MoS2 growth along the S-terminated edges: (F) without and (G) with Na adsorption; the blue, yellow, and
purple spheres represent Mo, S, and Na atoms, respectively. Reprinted with permission from Yang et al. (2018). Copyright 2018, The Authors.
2017a). Meanwhile, atomic resolution STEM has confirmed that alkali metals are not substitutionally doped
into the lattice of 2D TMDCs. Instead, they primarily adsorb on the surface of the 2D TMDCs in forms of
halide salts or alkali metal-containing byproducts (Lin et al., 2021). Therefore, any residual alkali metal-con-
taining compounds on the 2D TMDCs can be effectively removed during the wet transfer process in DI H2O
or IPA/H2O solution (Figure 5D).
It is worth noting that the excessive use of salts in SA-CVD can cause contamination and lead to inferior
growth of 2D TMDCs at worst. In such cases, the as-grown films have thick byproducts, weak PL, and
poor electrical performance compared to those grown under optimized conditions (Kang et al., 2015;
Kim et al., 2017). The negative effects of the excessive use of alkali metals were also observed in the recent
study on the CVD growth of MoSe2 monolayers using mixed molten salts, Na2MoO4–Na2SeO3. The intro-
duction of Na2SeO3 initially led to the enhanced growth of continuous MoSe2 films. However, as the con-
centration of Na+ (from Na2SeO3) increased, only isolated large MoSe2 flakes were grown (Li et al., 2021b).
Hence, using the optimal amount of alkali-metal content is vital to grow large-area, high-quality 2D TMDCs.
Apart from the addition of alkali metal halides or molten salts, substrates containing alkali metals, such as
soda-lime glass, which are primarily composed of SiO2, Na2O, and CaO, can also result in such enhanced
growth of 2D TMDCs. For example, Chen et al. achieved rapid growth of a large MoSe2 film with a domain
size of up to 2.5 mm in 5 min on a molten glass substrate (Chen et al., 2017a). The as-grown MoSe2 mono-
layers had a high carrier mobility of up to 95 cm2/Vs. However, as the glass substrate was in a ‘‘liquid state’’
at the high growth temperature of 1050 C—which is above the melting point of glass (1000 C)—droplet-
like curved surfaces and cracks were formed when the glass substrates cooled down to room temperature.
Subsequently, Yang et al. reported on the low-pressure CVD growth of 6-inch monolayer MoS2 films on
soda-lime glass at 720 C, which is slightly below the glass transition temperature of 730 C (Figure 5E)
(Yang et al., 2018). Partially oxidized Mo foil was loaded above the glass substrates to guarantee a uniform

iScience ll
Review OPEN ACCESS
supply of Mo precursor. This gave rise to a 6-inch monolayer MoS2 film with a large domain size of 400 mm
in 8 min. The high growth rate of MoS2 on glass substrates can be understood through DFT calculations. As
shown in Figures 5F and 5G, incorporating Na at the edge of the growing MoS2 reduces the energy barrier
for converting Mo2S2 to Mo2S4 from 0.53 eV to 0.29 eV. This lower energy barrier in the Na-assisted growth
of MoS2 monolayers increases the growth rate by a factor of 17 at 1000 K. Furthermore, the low-cost MoS2
films grown on glass substrates can be subjected to PMMA-mediated etching-free transfer onto rigid
substrates or roll-to-roll transfer onto flexible substates. Later, the authors further demonstrated the thick-
ness tunable growth of wedding-cake-like MoS2 flakes on soda-lime glass via NaCl-coated Mo foil (Yang
et al., 2019b). With the aid of NaCl, the vapor pressure of Mo precursor—MoOCl4 increases significantly
(Table 1j). Combined with the catalytic effect of Na from soda-lime glass, MoS2 tiers can be generated
layer-by-layer.
To avoid the high-cost low pressure CVD and the excess supply of TM precursors in atmospheric pres-
sure CVD, Cai et al. developed a ‘‘dissolution–precipitation’’ 2D TMDC growth process by sandwiching
molten salts between two glass substrates (Cai et al., 2021). First, Na2MoO4, Na2WO4, and NaVO3
aqueous solutions were spin-coated on a thick bottom glass substrate, and then covered with a thin glass
substrate. This combination of glass substrates and the Salt 2.0 technique provides a new approach to
ensure the uniform growth of 2D TMDCs and their alloys. Notably, choosing glass substrates with proper
glass transition temperatures (without deformation and maintain surface flatness) and thermal expansion
coefficients (to reduce strain and eliminate cracks) are critical to ensure the successful growth of high-
quality 2D TMDCs. In that sense, exploring novel growth substrates could be an important direction
to achieve controllable synthesis of 2D materials that deserves more research efforts (Qin et al., 2020).
PERSPECTIVE
2D materials, especially semiconducting 2D TMDCs, have received significant attention from academics
and semiconductor industry owing to their extraordinary electrical properties at monolayer (sub-nano-
meter) thickness. Intensive research on SA-CVD has demonstrated that it has significant potential for appli-
cation in future electronics (Li et al., 2020a; Sebastian et al., 2021; Shen et al., 2021; Wang et al., 2019b).
Depending on the growth modes, the SA-CVD has been generally categorized into the Salt 1.0 and Salt
2.0 techniques. Because each has its pros and cons as discussed here and other review articles (Han
et al., 2019; Jiang et al., 2019; Kim et al., 2019; Xie et al., 2020), more efforts should be attributed for under-
standing the kinetic processes and exact roles of halogens and alkali metals in the SA-CVD growth of 2D
TMDCs. Only with a more comprehensive knowledge obtained on the growth mechanisms of SA-CVD and
the exact requirements for target application, proper growth techniques can be designed. The following
are some promising aspects that deserve more research efforts in future.
1) Alkali-metal free growth of 2D TMDCs. To meet the critical requirements in electronics, it is of utmost
importance to achieve high purity growth with extreme crystallinity. Therefore, the TM precursors
have to be carefully chosen. For instance, metal organic precursors in the commonly used MOCVD
system often cause carbon contamination in the as-grown 2D TMDCs (Cohen et al., 2020). On the
other hand, the SA-CVD, which uses alkali-metal-free metal halides/oxyhalides (e.g., MoCl5, CrCl3,
FeCl2, MoOCl4, WO2Cl2, etc.), has proven promising to eliminate the detrimental effects of alkali
metals (Chu et al., 2019; Hu et al., 2021; Meng et al., 2021; Okada et al., 2014; Wang et al., 2021;
Zhang et al., 2019). Replacing the metal organic precursors with the TM halides/oxyhalides in the
MOCVD system could be a good alternative to realize high quality growth of 2D TMDC monolayers.
2) Low-temperature growth of 2D TMDCs. The low melting point and high vapor pressure of TM ha-
lides/oxyhalides is advantageous for low-temperature growth. This enables possible direct integra-
tion of 2D TMDCs on device wafers and even flexible substrates without transfer. In addition, it may
also allow the sequential growth of TMDC-based heterojunctions without causing thermal degrada-
tion or etching of the existing TMDCs grown. With that, high-quality TMDC-based van der Waals and
in-plane heterojunctions having ideal optical and electrical properties can be synthesized, and hence
extending their application in related fields.
3) Layer-controlled growth of 2D TMDCs. Few-layer 2D TMDCs are more robust channel materials of
FETs compared to their monolayer counterparts. This is due to their high mechanical and chemical
stability that are insensitive to the intense device fabrication process. Besides, the greater number of
layers also means they have more transport channels, granting them superior electrical performance

ll iScience
OPEN ACCESS Review
with high on-state current and carrier mobility. Because the epitaxial growth of a second TMDC layer
on preexisting one has been demonstrated using molten salts (e.g., Na2Mo2O7) (Chang et al., 2020;
Li et al., 2018), there is a great potential to achieve wafer-scale layer-controlled 2D TMDCs by depos-
iting these molten salts onto the TMDC monolayers as nucleation seeds and using TM halides/
oxyhalides as main growth precursors.
4) Patterned growth and controllable doping of 2D TMDCs. Molten salts (e.g., Na2MoO4, Na2MoO4)
and mixed molten salts (Na2WO4–NaVO3) have been employed to grow intrinsic semiconducting
2D TMDCs and metallic V-doped/alloyed 2D TMDCs, respectively. They are ideal channel and con-
tact/interconnecting materials for FETs and integrated circuits (ICs). Therefore, sophisticated 2D
TMDC-based ICs can be fabricated using prepatterned molten salts. Meanwhile, additional research
is required to explore the feasibility of using n-type dopants for growing metallic 2D TMDC alloys.
This would enable the fabrication of 2D TMDC-based CMOS with p-type and n-type van der Waals
contact or in-plane heterojunction, and further enrich the functionality of 2D TMDC-based ICs.
5) Wafer-scale growth of 2D TMDC single crystals. The synthesis of large-area TMDC single crystals
with unprecedented crystallinity, electrical quality, and wafer-scale uniformity is the ultimate target
that will eventually pave the way for 2D TMDC-based electronics (Li et al., 2021; Xu et al., 2021).
Molten salts such as Na2Mo2O7 had been used to achieve ledge-induced epitaxial growth of 1D
MoS2 nanoribbons along with the surface steps of NaCl crystals. Therefore, there is a great potential
to synthesize wafer-scale 2D TMDC single crystals via the stitching of parallel 1D TMDC nanoribbons,
which grow on engineered substrates with parallel surface steps using molten salts (Zhang et al.,
2021b).
CONCLUSIONS
Owing to the rapid development in SA-CVD, a great variety of 2D materials have been synthesized in recent
years. The roles of halogen and alkali metal in promoting the growth of 2D TMDCs are elaborated herein. In
general, halogens increase the volatility of the metal precursors, which have high melting points, to initiate
rapid VSS growth. In contrast, alkali metals liquefy and stabilize metal precursors to achieve VLS growth.
Based on the Salt 1.0 and Salt 2.0 techniques, new advanced synthetic methods could be anticipated to
realize the fabrication of perfect 2D TMDCs in future for a diverse application in electronics and
optoelectronics.
ACKNOWLEDGMENTS
S. Li acknowledges the support from JSPS-KAKENHI (21K04839) and ICYS. S. Li thanks H.E. Lim (Tokyo
Metropolitan University, Japan) and S. Liu (Hunan University, China) for the helpful discussion; and
X. Wang (National University of Singapore, Singapore) for preparing the illustration of Figure 1I.
REFERENCES
Arreola, V.M.A., Salazar, M.F., Zhang, T., Wang, Chang, M.-C., Ho, P.-H., Tseng, M.-F., Lin, F.-Y., Cohen, A., Patsha, A., Mohapatra, P.K., Kazes, M.,
K., Aguilar, A.H.B., Reddy, K.C.S., Strupiechonski, Hou, C.-H., Lin, I.-K., Wang, H., Huang, P.-P., Ranganathan, K., Houben, L., Oron, D., and
E., Terrones, M., and Bugallo, A.D.L. (2021). Chiang, C.-H., and Yang, Y.-C. (2020). Fast growth Ismach, A. (2020). Growth-etch metal–organic
Direct growth of monolayer 1T–2H MoS2 of large-grain and continuous MoS2 films through chemical vapor deposition approach of WS2
heterostructures using KCl-assisted CVD process. a self-capping vapor–liquid–solid method. Nat. atomic layers. ACS Nano 15, 526–538.
2D Mater. 8, 025033. Commun. 11, 3682.
Cun, H., Macha, M., Kim, H., Liu, K., Zhao, Y.,
Bai, X., Li, S., Das, S., Du, L., Dai, Y., Yao, L., Raju, Chen, J., Zhao, X., Tan, S.J., Xu, H., Wu, B., Liu, B., LaGrange, T., Kis, A., and Radenovic, A. (2019).
R., Du, M., Lipsanen, H., and Sun, Z. (2021). Single- Fu, D., Fu, W., Geng, D., and Liu, Y. (2017a). Wafer-scale MOCVD growth of monolayer MoS2
step chemical vapour deposition of anti-pyramid Chemical vapor deposition of large-size on sapphire and SiO2. Nano Res. 12, 2646–2652.
MoS2/WS2 vertical heterostructures. Nanoscale monolayer MoSe2 crystals on molten glass. J. Am.
13, 4537–4542. Chem. Soc. 139, 1073–1076. Fan, S., Yun, S.J., Yu, W.J., and Lee, Y.H. (2020).
Tailoring quantum tunneling in a
Chen, K., Chen, Z., Wan, X., Zheng, Z., Xie, F., vanadium-doped WSe2/SnSe2 heterostructure.
Cai, Z., Lai, Y., Zhao, S., Zhang, R., Tan, J., Feng, Chen, W., Gui, X., Chen, H., Xie, W., and Xu, J. Adv. Sci. 7, 1902751.
S., Zou, J., Tang, L., Lin, J., and Liu, B. (2021). (2017b). A simple method for synthesis of
Dissolution-precipitation growth of uniform and high-quality millimeter-scale 1T0 transition-metal Fu, L., Hu, D., Mendes, R.G., Rümmeli, M.H., Dai,
clean two dimensional transition metal telluride and near-field nanooptical properties. Q., Wu, B., Fu, L., and Liu, Y. (2018a). Highly
dichalcogenides. Natl. Sci. Rev. 8, nwaa115. Adv. Mater. 29, 1700704. organized epitaxy of Dirac semimetallic PtTe2
crystals with extrahigh conductivity and visible
Cai, Z., Shen, T., Zhu, Q., Feng, S., Yu, Q., Liu, J., Chu, J., Zhang, Y., Wen, Y., Qiao, R., Wu, C., He, surface plasmons at edges. ACS Nano 12, 9405–
Tang, L., Zhao, Y., Wang, J., and Liu, B. (2020). P., Yin, L., Cheng, R., Wang, F., and Wang, Z. 9411.
Dual-additive assisted chemical vapor deposition (2019). Sub-millimeter-scale growth of one-unit-
for the growth of Mn-doped 2D MoS2 with cell-thick ferrimagnetic Cr2S3 nanosheets. Nano Fu, Q., Wang, X., Zhou, J., Xia, J., Zeng, Q., Lv, D.,
tunable electronic properties. Small 16, 1903181. Lett. 19, 2154–2161. Zhu, C., Wang, X., Shen, Y., and Li, X. (2018b).

iScience ll
Review OPEN ACCESS
One-step synthesis of metal/semiconductor p-type Nb-doped WS2 monolayers. Chem. growth of large WSe2 and WS2 monolayer
heterostructure NbS2/MoS2. Chem. Mater. 30, Mater. 31, 3534–3541. crystals. Appl. Mater. Today 1, 60–66.
4001–4007.
Kang, K., Xie, S., Huang, L., Han, Y., Huang, P.Y., Li, T., Guo, W., Ma, L., Li, W., Yu, Z., Han, Z., Gao,
Furchi, M.M., Pospischil, A., Libisch, F., Mak, K.F., Kim, C.-J., Muller, D., and Park, J. S., Liu, L., Fan, D., and Wang, Z. (2021). Epitaxial
Burgdörfer, J., and Mueller, T. (2014). (2015). High-mobility three-atom-thick growth of wafer-scale molybdenum disulfide
Photovoltaic effect in an electrically tunable van semiconducting films with wafer-scale semiconductor single crystals on sapphire. Nat.
der Waals heterojunction. Nano Lett. 14, 4785– homogeneity. Nature 520, 656–660. Nanotechnol. 16. https://doi.org/10.1038/
4791. s41565-021-00963-8.
Kappera, R., Voiry, D., Yalcin, S.E., Branch, B.,
Gao, Z., Ji, Q., Shen, P.-C., Han, Y., Leong, W.S., Gupta, G., Mohite, A.D., and Chhowalla, M. Li, S., Hong, J., Gao, B., Lin, Y.C., Lim, H.E., Lu, X.,
Mao, N., Zhou, L., Su, C., Niu, J., and Ji, X. (2018). (2014). Phase-engineered low-resistance contacts Wu, J., Liu, S., Tateyama, Y., and Sakuma, Y.
In situ-generated volatile precursor for CVD for ultrathin MoS2 transistors. Nat. Mater. 13, (2021a). Tunable doping of rhenium and
growth of a semimetallic 2D dichalcogenide. ACS 1128–1134. vanadium into transition metal dichalcogenides
Appl. Mater. Inter. 10, 34401–34408. for two-dimensional electronics. Adv. Sci. 8,
Kazenas, E., Tsvetkov, Y.V., Astakhova, G., 2004438.
Han, S.W., Yun, W.S., Woo, W.J., Kim, H., Park, J., Volchenkova, V., and Ovchinnikova, O. (2010).
Hwang, Y.H., Nguyen, T.K., Le, C.T., Kim, Y.S., Thermodynamics of sodium molybdate Li, S., Lin, Y.-C., Hong, J., Gao, B., Lim, H.E., Yang,
and Kang, M. (2021). Interface defect engineering evaporation. Russian Metall. (Metally) 2010, X., Liu, S., Tateyama, Y., Tsukagoshi, K., and
of a large-scale CVD-grown MoS2 monolayer via 389–392. Sakuma, Y. (2021b). Mixed-salt enhanced
residual sodium at the SiO2/Si substrate. Adv. chemical vapor deposition of two-dimensional
Mater. Inter. 8, 2100428. Kim, H., Ovchinnikov, D., Deiana, D., Unuchek, D., transition metal dichalcogenides. Chem. Mater.
and Kis, A. (2017). Suppressing nucleation in 33, 7301–7308.
Han, G.H., Kybert, N.J., Naylor, C.H., Lee, B.S., metal–organic chemical vapor deposition of
Ping, J., Park, J.H., Kang, J., Lee, S.Y., Lee, Y.H., MoS2 monolayers by alkali metal halides. Nano Li, S., Lin, Y.-C., Liu, X.-Y., Hu, Z., Wu, J., Nakajima,
and Agarwal, R. (2015). Seeded growth of highly Lett. 17, 5056–5063. H., Liu, S., Okazaki, T., Chen, W., and Minari, T.
crystalline molybdenum disulphide monolayers (2019). Wafer-scale and deterministic patterned
at controlled locations. Nat. Commun. 6, 6128. Kim, M., Seo, J., Kim, J., Moon, J.S., Lee, J., Kim, growth of monolayer MoS2 via vapor–liquid–solid
J.-H., Kang, J., and Park, H. (2021). High- method. Nanoscale 11, 16122–16129.
Han, W., Liu, K., Yang, S., Wang, F., Su, J., Jin, B., crystalline monolayer transition metal
Li, H., and Zhai, T. (2019). Salt-assisted chemical dichalcogenides films for wafer-scale electronics. Li, S., Lin, Y.-C., Zhao, W., Wu, J., Wang, Z., Hu, Z.,
vapor deposition of two-dimensional materials. ACS Nano 15, 3038–3046. Shen, Y., Tang, D.-M., Wang, J., and Zhang, Q.
Sci. China Chem. 62, 1300–1311. (2018). Vapour–liquid–solid growth of monolayer
Kim, S.Y., Kwak, J., Ciobanu, C.V., and Kwon, S.Y. MoS2 nanoribbons. Nat. Mater. 17, 535–542.
(2019). Recent developments in controlled
Hoang, A.T., Shinde, S.M., Katiyar, A.K., Dhakal,
vapor-phase growth of 2D group 6 transition
K.P., Chen, X., Kim, H., Lee, S.W., Lee, Z., and Li, W., Huang, J., Han, B., Xie, C., Huang, X., Tian,
metal dichalcogenides. Adv. Mater. 31, 1804939.
Ahn, J.-H. (2018). Orientation-dependent optical K., Zeng, Y., Zhao, Z., Gao, P., and Zhang, Y.
characterization of atomically thin transition (2020b). Molten-salt-assisted chemical vapor
Kojima, K., Lim, H.E., Liu, Z., Zhang, W., Saito, T.,
metal ditellurides. Nanoscale 10, 21978–21984. deposition process for substitutional doping of
Nakanishi, Y., Endo, T., Kobayashi, Y., Watanabe,
monolayer MoS2 and effectively altering the
K., and Taniguchi, T. (2019). Restoring the intrinsic
Hu, D., Ye, C., Wang, X., Zhao, X., Kang, L., Liu, J., electronic structure and phononic properties.
optical properties of CVD-grown MoS2
Duan, R., Cao, X., He, Y., and Hu, J. (2021). Adv. Sci. 7, 2001080.
monolayers and their heterostructures.
Chemical vapor deposition of superconducting
Nanoscale 11, 12798–12803.
FeTe1–x Sex nanosheets. Nano Lett. 21, 5338– Li, X., Kahn, E., Chen, G., Sang, X., Lei, J.,
5344. Passarello, D., Oyedele, A.D., Zakhidov, D., Chen,
Lai, Z., He, Q., Tran, T.H., Repaka, D.M., Zhou,
D.-D., Sun, Y., Xi, S., Li, Y., Chaturvedi, A., and K.-W., and Chen, Y.-X. (2020c). Surfactant-
Hu, X., Huang, P., Jin, B., Zhang, X., Li, H., Zhou, Tan, C. (2021). Metastable 1T0 -phase group VIB mediated growth and patterning of atomically
X., and Zhai, T. (2018). Halide-induced self-limited transition metal dichalcogenide crystals. Nat. thin transition metal dichalcogenides. ACS Nano
growth of ultrathin nonlayered Ge flakes for high- Mater. 20, 1113–1120. 14, 6570–6581.
performance phototransistors. J. Am. Chem. Soc.
140, 12909–12914. Lee, C.-H., Lee, G.-H., Van Der Zande, A.M., Lin, Y.-C., Lee, S., Yang, Y.-C., Chiu, P.-W., Lee,
Chen, W., Li, Y., Han, M., Cui, X., Arefe, G., G.-D., and Suenaga, K. (2021). Two-dimensional
Huang, J.-K., Pu, J., Hsu, C.-L., Chiu, M.-H., Nuckolls, C., and Heinz, T.F. (2014). Atomically iodine-monofluoride epitaxy on WSe2. NPJ 2D
Juang, Z.-Y., Chang, Y.-H., Chang, W.-H., Iwasa, thin p–n junctions with van der Waals Mater. Appl. 5, 18.
Y., Takenobu, T., and Li, L.-J. (2014). Large-area heterointerfaces. Nat. Nanotechnol. 9, 676–681.
synthesis of highly crystalline WSe2 monolayers Ling, X., Lee, Y.-H., Lin, Y., Fang, W., Yu, L.,
and device applications. ACS Nano 8, 923–930. Lee, Y.H., Zhang, X.Q., Zhang, W., Chang, M.T., Dresselhaus, M.S., and Kong, J. (2014). Role of the
Lin, C.T., Chang, K.D., Yu, Y.C., Wang, J.T.W., seeding promoter in MoS2 growth by chemical
Huang, L., Thi, Q.H., Zheng, F., Chen, X., Chu, Chang, C.S., and Li, L.J. (2012). Synthesis of vapor deposition. Nano Lett. 14, 464–472.
Y.W., Lee, C.-S., Zhao, J., and Ly, T.H. (2020). large-area MoS2 atomic layers with chemical
Catalyzed kinetic growth in two-dimensional vapor deposition. Adv. Mater. 24, 2320–2325. Ling, X., Lin, Y., Ma, Q., Wang, Z., Song, Y., Yu, L.,
MoS2. J. Am. Chem. Soc. 142, 13130–13135. Huang, S., Fang, W., Zhang, X., and Hsu, A.L.
Li, J., Yang, X., Liu, Y., Huang, B., Wu, R., Zhang, (2016). Parallel stitching of 2D materials. Adv.
Ji, Q., Zhang, Y., Gao, T., Zhang, Y., Ma, D., Liu, Z., Zhao, B., Ma, H., Dang, W., and Wei, Z. (2020a). Mater. 28, 2322–2329.
M., Chen, Y., Qiao, X., Tan, P.-H., and Kan, M. General synthesis of two-dimensional van der
(2013). Epitaxial monolayer MoS2 on mica with Waals heterostructure arrays. Nature 579, Liu, C., Xu, X., Qiu, L., Wu, M., Qiao, R., Wang, L.,
novel photoluminescence. Nano Lett. 13, 3870– 368–374. Wang, J., Niu, J., Liang, J., and Zhou, X. (2019).
3877. Kinetic modulation of graphene growth by
Li, M.-Y., Shi, Y., Cheng, C.-C., Lu, L.-S., Lin, Y.-C., fluorine through spatially confined
Jiang, J., Li, N., Zou, J., Zhou, X., Eda, G., Zhang, Tang, H.-L., Tsai, M.-L., Chu, C.-W., Wei, K.-H., decomposition of metal fluorides. Nat. Chem. 11,
Q., Zhang, H., Li, L.-J., Zhai, T., and Wee, A.T. and He, J.-H. (2015a). Epitaxial growth of a 730–736.
(2019). Synergistic additive-mediated CVD monolayer WSe2–MoS2 lateral p-n junction with
growth and chemical modification of 2D an atomically sharp interface. Science 349, Liu, H., Qi, G., Tang, C., Chen, M., Chen, Y., Shu,
materials. Chem. Soc. Rev. 48, 4639–4654. 524–528. Z., Xiang, H., Jin, Y., Wang, S., and Li, H. (2020).
Growth of large-area homogeneous monolayer
Jin, Y., Zeng, Z., Xu, Z., Lin, Y.-C., Bi, K., Shao, G., Li, S., Wang, S., Tang, D.-M., Zhao, W., Xu, H., transition-metal disulfides via a molten liquid
Hu, T.S., Wang, S., Li, S., and Suenaga, K. (2019). Chu, L., Bando, Y., Golberg, D., and Eda, G. intermediate process. ACS Appl. Mater.
Synthesis and transport properties of degenerate (2015b). Halide-assisted atmospheric pressure Interfaces 12, 13174–13181.

ll iScience
OPEN ACCESS Review
Liu, K.-K., Zhang, W., Lee, Y.-H., Lin, Y.-C., Chang, liquid-phase precursor mixing. ACS Nano 13, Voiry, D., Mohite, A., and Chhowalla, M. (2015).
M.-T., Su, C.-Y., Chang, C.-S., Li, H., Shi, Y., and 10768–10775. Phase engineering of transition metal
Zhang, H. (2012). Growth of large-area and highly dichalcogenides. Chem. Soc. Rev. 44, 2702–2712.
crystalline MoS2 thin layers on insulating Radisavljevic, B., Radenovic, A., Brivio, J.,
substrates. Nano Lett. 12, 1538–1544. Giacometti, V., and Kis, A. (2011). Single-layer Voiry, D., Yamaguchi, H., Li, J., Silva, R., Alves,
MoS2 transistors. Nat. Nanotechnol. 6, 147–150. D.C., Fujita, T., Chen, M., Asefa, T., Shenoy, V.B.,
Liu, L., Wu, J., Wu, L., Ye, M., Liu, X., Wang, Q., and Eda, G. (2013). Enhanced catalytic activity in
Hou, S., Lu, P., Sun, L., and Zheng, J. (2018). Rasouli, H.R., Mehmood, N., Çakıro glu, O., and strained chemically exfoliated WS2 nanosheets
Phase-selective synthesis of 1T0 -MoS2 Kasırga, T.S. (2019). Real time optical observation for hydrogen evolution. Nat. Mater. 12, 850–855.
monolayers and heterophase bilayers. Nat. and control of atomically thin transition metal
Mater. 17, 1108–1114. dichalcogenide synthesis. Nanoscale 11, 7317– Vu, V.T., Vu, T.T.H., Phan, T.L., Kang, W.T., Kim,
7323. Y.R., Tran, M.D., Nguyen, H.T.T., Lee, Y.H., and
Liu, Y., Duan, X., Shin, H.-J., Park, S., Huang, Y., Yu, W.J. (2021). One-step synthesis of NbSe2/Nb-
and Duan, X. (2021). Promises and prospects of doped WSe2 metal/doped-semiconductor van
Sasaki, S., Kobayashi, Y., Liu, Z., Suenaga, K.,
two-dimensional transistors. Nature 591, 43–53. der Waals heterostructures for doping controlled
Maniwa, Y., Miyauchi, Y., and Miyata, Y. (2016).
Growth and optical properties of Nb-doped WS2 ohmic contact. ACS Nano 15, 13031–13040.
Ma, L., Zhu, J., Li, W., Huang, R., Wang, X., Guo,
monolayers. Appl. Phys. Express 9, 071201.
J., Choi, J.-H., Lou, Y., Wang, D., and Zou, G. Wang, D., Zhou, Y., Zhang, H., Zhang, R., Dong,
(2021). Immobilized precursor particle driven H., Xu, R., Cheng, Z., He, Y., and Wang, Z. (2020).
growth of centimeter-sized MoTe2 monolayer. Schmidt, P., Binnewies, M., Glaum, R., and
Schmidt, M. (2013). Chemical vapor transport Wafer-scale growth of pristine and doped
J. Am. Chem. Soc. 143, 13314–13324. monolayer MoS2 films for electronic device
reactions–methods, materials, modeling. Adv.
Top. Cryst. Growth, 227–305. applications. Inorg. Chem. 59, 17356–17363.
Meng, L., Zhou, Z., Xu, M., Yang, S., Si, K., Liu, L.,
Wang, X., Jiang, H., Li, B., and Qin, P. (2021). Wang, H., Chen, Y., Duchamp, M., Zeng, Q.,
Anomalous thickness dependence of Curie Sebastian, A., Pendurthi, R., Choudhury, T.H.,
Wang, X., Tsang, S.H., Li, H., Jing, L., Yu, T., and
temperature in air-stable two-dimensional Redwing, J.M., and Das, S. (2021). Benchmarking
Teo, E.H.T. (2018). Large-area atomic layers of the
ferromagnetic 1T-CrTe2 grown by chemical vapor monolayer MoS2 and WS2 field-effect transistors.
charge-density-wave conductor TiSe2. Adv.
deposition. Nat. Commun. 12, 809. Nat. Commun. 12, 693.
Mater. 30, 1704382.
Mo, H., Zhang, X., Liu, Y., Kang, P., Nan, H., Gu, X., Shao, G., Lu, Y., Hong, J., Xue, X.X., Huang, J., Xu,
Wang, H., Huang, X., Lin, J., Cui, J., Chen, Y., Zhu,
Ostrikov, K.K., and Xiao, S. (2019). Two- Z., Lu, X., Jin, Y., Liu, X., and Li, H. (2020).
C., Liu, F., Zeng, Q., Zhou, J., and Yu, P. (2017a).
dimensional alloying molybdenum tin disulfide Seamlessly splicing metallic SnxMo1-xS2 at MoS2
High-quality monolayer superconductor NbSe2
monolayers with fast photoresponse. ACS Appl. edge for enhanced photoelectrocatalytic
grown by chemical vapour deposition. Nat.
Mater. Inter. 11, 39077–39087. performance in microreactor. Adv. Sci. 7,
Commun. 8, 394.
2002172.
Najmaei, S., Liu, Z., Zhou, W., Zou, X., Shi, G., Lei,
Wang, P., Lei, J., Qu, J., Cao, S., Jiang, H., He, M.,
S., Yakobson, B.I., Idrobo, J.-C., Ajayan, P.M., and Shao, G., Xue, X.-X., Zhou, X., Xu, J., Jin, Y., Qi, S., Shi, H., Sun, X., Gao, B., and Liu, W. (2019a).
Lou, J. (2013). Vapour phase growth and grain Liu, N., Duan, H., Wang, S., and Li, S. (2019). Mechanism of alkali metal compound-promoted
boundary structure of molybdenum disulphide Shape-engineered synthesis of atomically thin growth of monolayer MoS2: eutectic
atomic layers. Nat. Mater. 12, 754–759. 1T-SnS2 catalyzed by potassium halides. ACS intermediates. Chem. Mater. 31, 873–880.
Nano 13, 8265–8274.
Naylor, C.H., Parkin, W.M., Gao, Z., Kang, H.,
Noyan, M., Wexler, R.B., Tan, L.Z., Kim, Y., Wang, Q.H., Kalantar-Zadeh, K., Kis, A., Coleman,
Shen, P.-C., Su, C., Lin, Y., Chou, A.-S., Cheng, J.N., and Strano, M.S. (2012). Electronics and
Kehayias, C.E., and Streller, F. (2017). Large-area C.-C., Park, J.-H., Chiu, M.-H., Lu, A.-Y., Tang,
synthesis of high-quality monolayer 1T0 -WTe2 optoelectronics of two-dimensional transition
H.-L., and Tavakoli, M.M. (2021). Ultralow contact metal dichalcogenides. Nat. Nanotechnol. 7,
flakes. 2D Mater. 4, 021008. resistance between semimetal and monolayer 699–712.
semiconductors. Nature 593, 211–217.
Naylor, C.H., Parkin, W.M., Ping, J., Gao, Z., Zhou,
Y.R., Kim, Y., Streller, F., Carpick, R.W., Rappe, Wang, X., Bian, C., He, Y., Guo, J., Zhang, P., Liu,
Song, J.-G., Ryu, G.H., Kim, Y., Woo, W.J., Ko, L., Wei, Y., Meng, L., Jiang, H., and Li, B. (2021).
A.M., and Drndic, M. (2016). Monolayer single- K.Y., Kim, Y., Lee, C., Oh, I.-K., Park, J., and Lee, Z.
crystal 1T0 -MoTe2 grown by chemical vapor Ultrathin FeTe nanosheets with tetragonal and
(2017). Catalytic chemical vapor deposition of hexagonal phases synthesized by chemical vapor
deposition exhibits weak antilocalization effect. large-area uniform two-dimensional
Nano Lett. 16, 4297–4304. deposition. Mater. Today 45, 35–43.
molybdenum disulfide using sodium chloride.
Nanotechnology 28, 465103. Wang, Y., Kim, J.C., Wu, R.J., Martinez, J., Song,
Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang,
D., Zhang, Y., Dubonos, S.V., Grigorieva, I.V., and X., Yang, J., Zhao, F., Mkhoyan, A., Jeong, H.Y.,
Su, S.-K., Chuu, C.-P., Li, M.-Y., Cheng, C.-C., and Chhowalla, M. (2019b). Van der Waals
Firsov, A.A. (2004). Electric field effect in
Wong, H.-S.P., and Li, L.-J. (2021). Layered contacts between three-dimensional metals and
atomically thin carbon films. Science 306,
semiconducting 2D materials for future transistor two-dimensional semiconductors. Nature 568,
666–669.
applications. Small Struct. 2, 2000103. 70–74.
Novoselov, K.S., Jiang, D., Schedin, F., Booth, T.,
Khotkevich, V., Morozov, S., and Geim, A.K. Sung, J.H., Heo, H., Si, S., Kim, Y.H., Noh, H.R., Wang, Z., Xie, Y., Wang, H., Wu, R., Nan, T., Zhan,
(2005). Two-dimensional atomic crystals. Proc. Song, K., Kim, J., Lee, C.-S., Seo, S.-Y., and Kim, Y., Sun, J., Jiang, T., Zhao, Y., and Lei, Y. (2017b).
Natl. Acad. Sci. 102, 10451–10453. D.-H. (2017). Coplanar semiconductor–metal NaCl-assisted one-step growth of MoS2–WS2 in-
circuitry defined on few-layer MoTe2 via plane heterostructures. Nanotechnology 28,
Okada, M., Sawazaki, T., Watanabe, K., Taniguch, polymorphic heteroepitaxy. Nat. Nanotechnol. 325602.
T., Hibino, H., Shinohara, H., and Kitaura, R. 12, 1064–1070.
(2014). Direct chemical vapor deposition growth Xie, C., Yang, P., Huan, Y., Cui, F., and Zhang, Y.
of WS2 atomic layers on hexagonal boron nitride. Tan, J., Li, S., Liu, B., and Cheng, H.-M. (2021). (2020). Roles of salts in the chemical vapor
ACS Nano 8, 8273–8277. Structure, preparation, and applications of 2D deposition synthesis of two-dimensional
material-based metal–semiconductor transition metal chalcogenides. Dalton Trans. 49,
Qin, B., Ma, H., Hossain, M., Zhong, M., Xia, Q., Li, heterostructures. Small Struct. 2, 2000093. 10319–10327.
B., and Duan, X. (2020). Substrates in the synthesis
of two-dimensional materials via chemical vapor Tang, L., Xu, R., Tan, J., Luo, Y., Zou, J., Zhang, Z., Xu, D., Chen, W., Zeng, M., Xue, H., Chen, Y.,
deposition. Chem. Mater. 32, 10321–10347. Zhang, R., Zhao, Y., Lin, J., and Zou, X. (2021). Sang, X., Xiao, Y., Zhang, T., Unocic, R.R., and
Modulating electronic structure of monolayer Xiao, K. (2018). Crystal-field tuning of
Qin, Z., Loh, L., Wang, J., Xu, X., Zhang, Q., Haas, transition metal dichalcogenides by photoluminescence in two-dimensional materials
B., Alvarez, C., Okuno, H., Yong, J.Z., and Schultz, substitutional Nb-doping. Adv. Funct. Mater. 31, with embedded lanthanide ions. Angew. Chem.
T. (2019). Growth of Nb-doped monolayer WS2 by 2006941. Int. Ed. 57, 755–759.

iScience ll
Review OPEN ACCESS
Xu, X., Pan, Y., Liu, S., Han, B., Gu, P., Li, S., Xu, W., Zhan, Y., Liu, Z., Najmaei, S., Ajayan, P.M., and Zhang, K., Bersch, B.M., Zhang, F., Briggs, N.C.,
Peng, Y., Han, Z., and Chen, J. (2021). Seeded 2D Lou, J. (2012). Large-area vapor-phase growth Subramanian, S., Xu, K., Chubarov, M., Wang, K.,
epitaxy of large-area single-crystal films of the van and characterization of MoS2 atomic layers on a Lerach, J.O., and Redwing, J.M. (2018).
der Waals semiconductor 2H MoTe2. Science SiO2 substrate. Small 8, 966–971. Considerations for utilizing sodium chloride in
372, 195–200. epitaxial molybdenum disulfide. ACS Appl.
Zhang, D., Wen, C., Mcclimon, J.B., Masih Das, P., Mater. Interfaces 10, 40831–40837.
Yang, P., Yang, A.-G., Chen, L., Chen, J., Zhang, Zhang, Q., Leone, G.A., Mandyam, S.V., Drndic,
Y., Wang, H., Hu, L., Zhang, R.-J., Liu, R., and Qu, M., Johnson, A.T.C., Jr., and Zhao, M.Q. (2021a). Zhang, Y., Chu, J., Yin, L., Shifa, T.A., Cheng, Z.,
X.-P. (2019a). Influence of seeding promoters on Rapid growth of monolayer MoSe2 films for large- Cheng, R., Wang, F., Wen, Y., Zhan, X., and Wang,
the properties of CVD grown monolayer srea rlectronics. Adv. Electron. Mater. 7, 2001219. Z. (2019). Ultrathin magnetic 2D single-crystal
molybdenum disulfide. Nano Res. 12, 823–827. CrSe. Adv. Mater. 31, 1900056.
Zhang, L., Dong, J., and Ding, F. (2021b).
Yang, P., Zhang, Z., Sun, M., Lin, F., Cheng, T., Shi, Strategies, status, and challenges in wafer scale Zhang, Y., Yin, L., Chu, J., Shifa, T.A., Xia, J.,
J., Xie, C., Shi, Y., Jiang, S., and Huan, Y. (2019b). single crystalline two-dimensional materials Wang, F., Wen, Y., Zhan, X., Wang, Z., and He, J.
Thickness tunable wedding-cake-like MoS2 flakes synthesis. Chem. Rev. 121, 6321–6372. (2018). Edge-epitaxial growth of 2D NbS2-WS2
for high-performance optoelectronics. ACS Nano lateral metal-semiconductor heterostructures.
13, 3649–3658. Zhang, L., Wang, C., Liu, X.-L., Xu, T., Long, M., Adv. Mater. 30, 1803665.
Liu, E., Pan, C., Su, G., Zeng, J., and Fu, Y. (2017a).
Damage-free and rapid transfer of CVD-grown
Yang, P., Zou, X., Zhang, Z., Hong, M., Shi, J., two-dimensional transition metal Zhou, J., Lin, J., Huang, X., Zhou, Y., Chen, Y., Xia,
Chen, S., Shu, J., Zhao, L., Jiang, S., and Zhou, X. dichalcogenides by dissolving sacrificial water- J., Wang, H., Xie, Y., Yu, H., and Lei, J. (2018). A
(2018). Batch production of 6-inch uniform soluble layers. Nanoscale 9, 19124–19130. library of atomically thin metal chalcogenides.
monolayer molybdenum disulfide catalyzed by Nature 556, 355–359.
sodium in glass. Nat. Commun. 9, 979.
Zhang, L., Wang, G., Zhang, Y., Cao, Z., Wang, Y.,
Cao, T., Wang, C., Cheng, B., Zhang, W., and Zou, J., Cai, Z., Lai, Y., Tan, J., Zhang, R., Feng, S.,
Yu, Y., Nam, G.-H., He, Q., Wu, X.-J., Zhang, K., Wan, X. (2020). Tuning electrical conductance in Wang, G., Lin, J., Liu, B., and Cheng, H.-M. (2021).
Yang, Z., Chen, J., Ma, Q., Zhao, M., and Liu, Z. bilayer MoS2 through defect-mediated interlayer Doping concentration modulation in vanadium-
(2018). High phase-purity 1T0 -MoS2-and 1T0 - chemical bonding. ACS Nano 14, 10265–10275. doped monolayer molybdenum disulfide for
MoSe2 layered crystals. Nat. Chem. 10, 638–643. synaptic transistors. ACS Nano 15, 7340–7347.
Zhang, Q., Xiao, Y., Zhang, T., Weng, Z., Zeng, M.,
Yun, S.J., Duong, D.L., Ha, D.M., Singh, K., Phan, Yue, S., Mendes, R.G., Wang, L., Chen, S., and Zuo, Y., Yu, W., Liu, C., Cheng, X., Qiao, R., Liang,
T.L., Choi, W., Kim, Y.M., and Lee, Y.H. (2020). Rümmeli, M.H. (2017b). Iodine-mediated J., Zhou, X., Wang, J., Wu, M., and Zhao, Y. (2020).
Ferromagnetic order at room temperature in chemical vapor deposition growth of metastable Optical fibres with embedded two-dimensional
monolayer WSe2 semiconductor via vanadium transition metal dichalcogenides. Chem. Mater. materials for ultrahigh nonlinearity. Nat.
dopant. Adv. Sci. 7, 1903076. 29, 4641–4644. Nanotechnol. 15, 987–991.

1 s2.0 S2589004221011974 Main

Uploaded by

Copyright:

Available Formats

1 s2.0 S2589004221011974 Main

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1 s2.0 S2589004221011974 Main

Uploaded by

Copyright:

Available Formats

iScience ll

iScience 24, 103229, November 19, 2021 ª 2021 The Author(s). 1

Growth mechanism of halide salt-assisted CVD (HSA-CVD) of 2D TMDCs

Role of halogens in HSA-CVD

Role of alkali metals in HSA-CVD

2 iScience 24, 103229, November 19, 2021

Figure 1. Mechanism of HSA-CVD growth of 2D TMDCs

iScience 24, 103229, November 19, 2021 3

Table 1. Possible reactions in CVD growth of 2D TMDCs

Definition of Salt 1.0 and Salt 2.0 growth techniques

4 iScience 24, 103229, November 19, 2021

Applications of HSA-CVD (Salt 1.0 technique)

Versatility in growing 2D materials

iScience 24, 103229, November 19, 2021 5

Figure 2. Applications of HSA-CVD (Salt 1.0 technique)

6 iScience 24, 103229, November 19, 2021

iScience 24, 103229, November 19, 2021 7

Figure 3. Evolution of HSA-CVD

Upgrading of HSA-CVD (Salt 1.0 + technique)

8 iScience 24, 103229, November 19, 2021

Applications of molten salt-CVD (Salt 2.0 technique)

iScience 24, 103229, November 19, 2021 9

Figure 4. Application of molten salt-CVD (Salt 2.0 technique)

10 iScience 24, 103229, November 19, 2021

Alkali metals—two sides of the same coin

iScience 24, 103229, November 19, 2021 11

Figure 5. Alkali metals in the CVD growth of 2D TMDCs

12 iScience 24, 103229, November 19, 2021

iScience 24, 103229, November 19, 2021 13

14 iScience 24, 103229, November 19, 2021

iScience 24, 103229, November 19, 2021 15

16 iScience 24, 103229, November 19, 2021

iScience 24, 103229, November 19, 2021 17

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.