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2D Metallic Transition-Metal Dichalcogenides: Structures,

Synthesis, Properties, and Applications
Bei Zhao, Dingyi Shen, Zucheng Zhang, Ping Lu, Mongur Hossain, Jia Li, Bo Li,
and Xidong Duan*

chalcogen atom including S, Se, or Te) have

2D materials and the associated heterostructures define an ideal material recently drawn intense scientific and engi-
platform for investigating physical and chemical properties, and exhibiting neering interest because of the advantages
new functional applications in (opto)electronic devices, electrocatalysis, of diverse crystal structures, ultrathin thick-
and energy storage. 2D transition metal dichalcogenides (2D TMDs), as a ness, layer-dependent band gap, as well as
member of the 2D materials family including 2D semiconducting TMDs new functional applications in electronics,
optoelectronics, catalysis, energy storage,
(s-TMDs) and 2D metallic/semimetallic TMDs (m-TMDs) have attracted con-
and many others.[21–26] Moreover, TMDs are
siderable attention in the scientific community. Over the past decade, the 2D usually classified into four types according
s-TMDs have been extensively researched and reviewed elsewhere. Because to electronic band structures: metallic
of their distinctive physical properties including intrinsic magnetism, charge- TMDs, semimetallic TMDs, semicon-
density-wave order and superconductivity, and potential applications, such ducting s-TMDs with various energy band
gaps, and insulating TMDs. It is important
as high-performance electronic devices, catalysis, and as metal electrode
to note that semimetals have metallic prop-
contacts, 2D m-TMDs have grabbed widespread attention in recent years. erties in some cases, so we will summarize
However, reviews demonstrating the m-TMDs systematically and comprehen- metallic TMDs and semimetallic TMDs as
sively have been rarely reported. Here, the recent advances in 2D m-TMDs m-TMDs in this review.
in the aspects of their unique structures, synthetic approaches, distinctive Despite considerable efforts and a lot of
physical properties, and functional applications are highlighted. Finally, the successful examples in TMDs to date, the
vast majority of researches are still focused
current challenges and perspectives are discussed.
on s-TMDs and their heterostructures.
The s-TMDs display totally exotic physical
properties enabling a new generation of
1. Introduction electronic, photoelectric and spintronic devices. Compared with
s-TMDs, m-TMDs such as TaS2, NbSe2, and TiSe2 have aroused
Compared to bulk counterparts, 2D materials possess unusual worldwide research interest due to their exotic physical proper-
properties and promising applications owing to the reducing ties and potential applications in different fields. In the last few
dimensionality and/or quantum confinement effect.[1–6] 2D mate- years, m-TMDs have been manifested possessing a wealth of
rials have been rapidly expanded to graphene,[7,8] hexagonal boron exotic physical properties,[27] such as charge density wave (CDW)
nitride (BN),[9,10] black phosphorus,[11] borophene,[12] silicene,[13,14] of 1T-TaS2,[28] superconducting (SC) of 2H-NbSe2,[29] and mag-
and transition metal dichalcogenides (TMDs).[15–20] As the key netism of 1T-CrSe, CrSe2,[30,31] Weyl semimetals of 1Td-MoTe2,[32]
members of 2D materials, TMDs with the formula MX2 (where metallic monoclinic 1T′-MoTe2,[33,34] and Dirac semimetals of
M is a transition metal atom of group IV–VIII and X is the 1T-PtTe2.[35] As far as we know, CDW is a long-term problem
that has plagued researchers in condensed matter physics, this
unique 2D m-TMDs provide a rich material system to explore
B. Zhao, D. Y. Shen, Z. C. Zhang, P. Lu, M. Hossain, J. Li, B. Li, X. D. Duan the origins of superconductivity and CDW. These 2D m-TMDs
Hunan Key Laboratory of Two-Dimensional Materials
State Key Laboratory for Chemo/Biosensing and Chemometrics exhibit the high CDW phase transitions, which achieve a variety
College of Chemistry and Chemical Engineering of functional applications in high-performance electronic devices,
Hunan University such as oscillators, ultrafast memories, and logic circuits.[24]
Changsha 410082, China Furthermore, m-TMDs having high electrical conductivity and
E-mail: [email protected]
tunable thicknesses are more suitable for applications in metal
B. Li
electrodes contacts, and energy conversion/storage related fields.
School of Physics and Electronics
Hunan University More importantly, among all TMDs, m-TMDs present superior
Changsha 410082, China performance for electrocatalysis owing to their high electrical con-
ductivity and abundant catalytic active sites, which is beneficial to
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202105132.
promote electrode kinetics and improve catalytic performance.
The different physical properties of m-TMDs largely depend
DOI: 10.1002/adfm.202105132 on their crystal and electronic structures. For example, when

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Figure 1. Schematic illustration of typical band structures of TMDs in k-space and types of metals involved in TMDs. a) Insulator, b) semiconductor,
c) metal, and d) semimetal.

the phase of NbS2 transforms from 2H to 3R, the supercon- 2. Crystal and Electronic Structures
ductivity disappears;[36] By switching the phase from 2H to 3R
in TaSe2, the superconductivity transition temperature can be 2.1. General Band Structures of 2D TMDs
increased by nearly an order in magnitude (from 0.2 to 1.6 K).[37]
Recent progress has also revealed most of the m-TMDs own Different types of TMDs, such as metals, semimetals, semi-
extended five structures such as 1T,[38] 1T′,[39] 1Td,[40] 2H,[41] and conductors, and insulators, have different energy band struc-
3R.[37] To promote the applications of m-TMDs, it is essen- tures. Generally, s-TMDs and insulating TMDs have a band gap
tial to find a suitable synthesis method to prepare large-area between the conduction band bottom and valence band top, and
and high-quality m-TMDs. Several attempts have been used the Fermi level (Ef ) is located in the band gap (Figure 1a,b).[56,57]
to fabricate 2D m-TMDs such as mechanical exfoliation,[42–44] Metals have an appreciable density of states at the Ef because
chemical exfoliation,[45,46] molecular beam epitaxy (MBE),[47,48] the conduction band is partially filled (Figure 1c).[58] The top of
hydrothermal method,[49,50] salt-templating synthesis,[51] topo- the valence band and the bottom of the conduction band have a
chemical transformation,[52] and chemical vapor deposition small overlap in semimetals (Figure 1d). A semimetal thus has
(CVD). From a synthetic perspective, some significant progress no band gap and a negligible density of states at the Ef.[59] If a
has been made in the preparation of m-TMDs by CVD.[53–55] Weyl/Dirac node happens to sit on the Fermi surface, a “topo-
The CVD method demonstrates unique superiority in the syn- logical semimetal” whose Fermi surface is reduced to a Fermi
thesis of 2D m-TMDs with the large area, tunable thickness, point with a zero energy gap and a linear energy dispersion
and high-quality. By systematically controlling the experimental occurs. The two most representative members of topological
conditions including temperature, chamber pressure, flow rate, semimetals are Dirac semimetal and Weyl semimetal, whose
and various substrates, we can regulate the layer thicknesses, electron energy is linearly related to lattice momentum.[60] Such
phases, lateral sizes, and orientation of m-TMDs. However, the topological semimetal exhibits wonderful physical properties,
comprehensive review on m-TMDs is still scarce. such as the Fermi arcs in surface state, the magnetic unipole
In the past few years, there are a number of significant in momentum space, unique transport properties, magnetism,
reports focused on the growth of m-TMDs and some achieve- and so on, which have emerged as a highly exciting material
ments have been made in the in scientific and engineering system for exotic devices such as next generation spintronic
field. However, a comprehensive review of m-TMDs including devices, ultrafast memories, and quantum computing.[61–64]
the structures, synthesis, properties, and applications is rarely
reported. Here, we summarize the state-of-the-art progress of
m-TMDs in the aforementioned research aspects. First, the 2.2. The Crystal Structures and Electronic Structures
electronic structures and corresponding crystal structures of 2D m-TMDs
including 1T, 1T′, 1Td, 2H, and 3R of typical layered m-TMDs are
introduced and their synthetic methods for creating m-TMDs The physical properties of 2D m-TMDs are strongly correlated
are discussed in detail. Then, we highlight the novel physical with their crystal structures and electronic structures, a deep
properties and potential applications of m-TMDs. Finally, we understanding of crystal structures of 2D m-TMDs is crucial.
put forward some views on the development, challenges, and The two basic phases of 2D m-TMDs with MX2 chemical for-
potential opportunities of m-TMDs. mula are the H phase (2H and 3R) and T phase (1T, 1T′, and

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Figure 2. The atomic structures of m-TMDs. Two primary phases of 2D TMDs: a) T phase and b) H phase. c) The ball-and-stick models of five kinds
of phase structures in 2D m-TMDs.

1Td), respectively. Figure 2a,b show the ball-and-stick models of from the perfect octahedral coordination in the 1T phase and
T phase and H phase, in which blue and pink balls represent arrange in a zigzag way along the [010] direction.[71] However,
transition metals (M) and chalcogens (X), respectively. The H in 1Td-TMDs, a transition metal chain is formed in the dichal-
phase is a trigonal prismatic structure (D3h group), which is cogenide layer along the orthogonal unit cell axis, which makes
constructed by symmetrically arranging the upper and lower the compound present a 1D structure. Figure 3c shows the
tetrahedron with the metal surface (center) as the symmetry high-magnification HAADF-STEM image and simulated STEM
point (Figure 2b). Meantime, in Figure 2a, the T phase is an image of 1Td-MoTe2 nanosheet arranging viewed along [001]
octahedral structure (D3d group), which is formed by rotating zone.[72] Moreover, the Td structure is also found in WTe2.[73]
the lower or upper tetrahedron by 180°. The d orbitals of M The phases of 2H and 3R can be obtained by the stacking the
atoms are split into two levels (two degenerated orbitals of single-layer phase of H in the sequence of ABA and ABC, respec-
dx2−y2,z2 and three degenerated orbitals of dxy,yz,zx) for T phase tively. The top view of 2H m-TMD which belong to P63/mmc
and three levels (two degenerated orbitals of dxy,yz, two degen- presents a hexagonal lattice formed by alternating two stacked
erated orbitals of dx2−y2,xy, and orbital of dz2) for H phase, X atoms and one M atom. Most 2H phase TMDs are semicon-
respectively.[65,66] ductor, but a few TMDs such as 2H-NbS2, 2H-TaS2, 2H-NbSe2,
Figure 2c displays the top views and side views of five kinds and 2H-TaSe2, are metal.[74–77] The atomic resolution annual
of phases. The 1T phase (primary structure) belongs to the hex- dark-field STEM image and the simulated atom of metallic
agonal group (P3–m1), in which one of the X layers is shifted 2H-NbSe2 in Figure 3d, demonstrates the hexagonal atomic
compared to the other led to the XMX′ stacking sequence. lattice with alternating bright and dark spots corresponding
The atomic-resolution high angle annular dark field scanning to the Nb and Se atoms, respectively.[77] Figure 3e,f show the
transmission electron microscope (HAADF-STEM) image of HADDF-STEM images and the simulated STEM images with
typical 1T phase structure of NiTe2 is shown in Figure 3a, in corresponding structure models of 2H and 3R-TaSe2, respec-
which each hexagonal arrangement of Ni atom is surrounded tively. Unlike 2H-TaSe2, the stacking order of 3R-TaSe2 takes
by six Te atoms to form a hexagon.[38] The majority of 1T phase a staggered configuration, and additional atoms appear in the
TMDs exhibit metallic properties, a very small percentage of center of each honeycomb.[37]
1T phase TMDs are semiconductors. For instance, the indirect Table 1 illustrates the main 2D m-TMDs in a periodic table,
band gap 1T-HfS2 is ≈1.45 eV[67] and the band gap of 1T-HfSe2 in which the m-TMDs are formed by the combination of transi-
is ≈1.1 eV.[68] The 1T′ phase (distorted octahedral) and 1Td phase tion metals including the group IVB (Ti, Zr, and Hf), VB (V,
(orthorhombic) always have been formed by the distortion of Nb, and Ta), VIB (Cr, Mo, and W), VIII (Fe, Co, Ni, Pd, and
the 1T phase (octahedral configuration).[69–71] In the struc- Pt), and chalcogens including S, Se, and Te. Various band struc-
ture of 1T′-MoTe2 (Figure 3b), the Mo and Te atoms displace tures of MX2 in the same group can be attributed to the relative

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Figure 3. The typical atomic structures of m-TMDs. a) 1T-NiTe2. Reproduced with permission.[38] Copyright 2018, American Chemical Society.
b) 1T′-MoTe2. Reproduced with permission.[71] Copyright 2017, Springer Nature. c) 1Td-MoTe2. Reproduced with permission.[72] Copyright 2019, Springer
Nature. d) 2H-NbSe2. Reproduced with permission.[77] Copyright 2017, Springer Nature. e) 2H-TaSe2. f) Bilayer and trilayer 3R-TaSe2. Reproduced with
permission.[37] Copyright 2020, American Chemical Society.

Table 1. Main metallic (black) and semimetallic (red) TMDs in a periodic table TMD.

IVB VB VIB VIIB VIII

22Ti 23V 24Cr 26Fe 27Co 28Ni

(d2s2) (d3s2) (d5s1) (d6s2) (d7s2) (d8s2)

TiS2 (1T) VS2 (1T) FeS2 (1T) CoS/CoS2 (1T) NiS2 (1T)
TiSe2 (1T) VSe2 (1T) CrSe/CrSe2 (1T) FeSe/FeSe2 (1T) CoSe/CoSe2 (1T) NiSe/NiSe2 (1T)
TiTe2 (1T) VTe2 (1T) CrTe2 (1T) FeTe/FeTe2 (1T) CoTe2 (1T) NiTe2 (1T)
40Zr 41Nb 42Mo 46Pd

(d2s2) (d4s1) (d5s1) (d10)

NbS2 (1T,2H,3R) MoS2(1T)
NbSe2 (1T,2H,3R) MoSe2(1T)
ZrTe2 (1T) NbTe2 (1T) MoTe2 (1Td,1T′) PdTe2 (1T)
72Hf 73Ta 74W 78Pt

(d2s2) (d3s2) (d4s2) (d9s1)

TaS2 (1T,2H,3R)
TaSe2 (1T,2H,3R) PtSe2 (1T)
HfTe2 (1T) TaTe2 (1T,1T′) WTe2 (1Td,1T′) PtTe2 (1T)

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energy difference of metals and chalcogens. For the transition Table 2. The band gap of the PdX2 and PtX2 (X = S, Se, and Te)
metals (Ti, Zr, and Hf) in group IVB, their electron configu- (1L: monolayer, EL: even number of layers, OL: odd number of layers).
ration is d2s2. The m-TMDs formed by the group IVB transi-
tion metals and chalcogens have the 1T phase. Theoretically, Material Space group Bandgap
the combination of Ti, Zr, Hf, and chalcogens can easily form PdS2[93] Bulk: Pbca (#61) D2h 1L: ≈1.6 eV, bulk: 0 eV
the semiconducting TMDs owing to the even number (10) of EL: Pca21(#29) C2v (mm2)
valence electrons in the primitive unit cell, such as ZrS2, ZrSe2, OL: P21/c (#14) C2h (2/m)
HfS2, and HfSe2.[78] In addition, TiS2, TiSe2, TiTe2, ZrTe2, and PdSe2[94] 1L: ≈1.3 eV, bulk: 0 eV
HfTe2 are semimetals, which can be attribute to a small overlap PtS2[95]
1L: ≈1.6 eV, bulk: 0.25 eV
between the chalcogen valence band top of the p-orbital and the
PtSe2[96] 1L: ≈1.2 eV, bulk: 0 eV
transition metal conduction band bottom of the d-orbital.[79–83]
For the group VB transition metals (V, Nb, and Ta), m-TMDs PdTe2[97] Bulk: P3(−)m1 (#164) D3d Type-II Dirac semimetal
1L: P3(−)m1 (#164) D3d
that combined by VB transition metals and chalcogens
demonstrate metallic behavior because the number of electrons PtTe2[98] Type-II Dirac semimetal
in their orbits is odd.[78] VX2 only has a stable 1T phase, while
NbX2 and TaX2 have not only 1T phase but also 2H and 3R reported a transition from a metal to a semiconductor for thick-
phases. For some m-TMDs, the 1T phase is not stable at room nesses of PtSe2 lower than 2.5 nm.[100]
temperature, which can transform into distorted phases. For
example, the properties of 1T phase NbSe2 need to be meas-
ured under high temperatures.[84] For the group VIB transition 3. Synthetic Methods
metals (Cr, Mo, and W), the electron configuration of Cr and
Mo is d5s1, while W is d4s2. CrX2 is a metallic TMDs with a 1T To date, 2D m-TMDs can be constructed by CVD, mechan-
metastable phase.[85] In contrast, MoX2 and WX2 are semicon- ical exfoliation, chemical exfoliation, MBE, hydrothermal
ductors with 2H stable phase at room temperature except for method, salt-templating synthesis, topochemical transforma-
MoTe2 and WTe2 with Td and T′ phases. Moreover, 1T′ phase tion, the methods of phase transition from semiconductor
and 1Td phase can be converted to each other via adjusting the to metal by post-treatments, and so on. Here we mainly
experimental parameters such as temperature, pressure, and introduce the synthetic method of CVD, followed by a brief
Te vacancy.[86] It is worth noting that some m-TMDs formed summary of other synthetic methods. CVD method shows
by transition metal and chalcogen atoms with a stoichiometric unique superiority in the synthesis of m-TMDs with high-
ratio of 1:1 have a tetragonal structure (P4/nmm) such as FeSe, quality, tunable thickness, and large-area which defines a
FeTe, CoSe, and so on.[87–89] material platform for basic research and practical applica-
tions. The synthesis parameters of 2D m-TMDs by CVD are
illustrated in Table 3. Here, we present salt-assisted CVD
2.3. Layer-Dependent Band Structures synthesis at first. Then, we review the controllable synthesis
of m-TMDs grown by adjusting growth parameters. Finally,
The thickness of m-TMDs plays a significant role in the band we summarize the synthesis of heterostructures based on
structures and physical properties.[90–92] For instance, Chiang et al. m-TMDs.
investigated that as the thickness of TiSe2 film increases from
1 to 6 layers, more quantum well valence states emerge.[91] The
effect of interlayer interactions in m-TMDs combined with tran- 3.1. Chemical Vapor Deposition
sition metals (Ni, Pd, and Pt) and chalcogens (S, Se, and Te) is
more obvious. The d-orbitals of transition metal in Ni, Pd, and Pt 3.1.1. Salt-Assisted CVD Growth of 2D m-TMDs
are almost completely occupied, and the corresponding pz-orbital
of interlayer chalcogen atoms is highly hybridized, resulting in In the CVD method, metal oxides and metals are primarily
the dependence of physical properties on the number of layers. used as precursor materials for the growth of TMDs. But the
The band gap of MX2 (M = Pd, Pt; X = S, Se, and Te) are sum- synthesis of many m-TMDs is difficult because their precur-
marized in Table 2.[93–98] As the thickness of the PdSe2, PtS2, and sors including metals and metal oxides usually have relatively
PtSe2 reduces from bulk to monolayer, the metallic nature is high melting points and low vapor pressure which limits the
transformed into semiconducting characteristics. In Figure 4a, reaction especially for IVB group and VB group transition
the monolayer PdSe2 exhibits a ≈1.3 eV indirect band gap and metal oxides (TiO2: 1850 °C, Nb2O3: 1780 °C, Nb2O5: 1485 °C,
there is no band gap for the bulk PdSe2. The optical band gaps and Ta2O5: 1800 °C). To solve this issue, salt-assisted CVD is
versus the number of PdSe2 layers are also shown in the inset of introduced. Since this salt-assisted method was first applied
Figure 4b. As the thickness of PdSe2 increasing from monolayer to the synthesis of semiconducting WS2 and WSe2 monolayer
to bulk, the band gap decreases from ≈1.3 to 0 eV (within the in 2015,[135] this method plays a major role in the synthesis of
uncertainty of ±0.2 eV).[94] The layer-dependent band structure m-TMDs (Table 3). The molten salts can reduce the melting
and band gap evaluation of PtSe2 by first-principles calculations points of the metal oxides precursors and react with cer-
are shown in Figure 4c. The monolayer PtSe2 is semiconductor tain metal oxides to form oxychlorides, thereby increase the
with the indirect band gap of ≈1.2 eV, while the thicker layers of overall reaction rate.[53] Figure 5a illustrates the mechanism of
PtSe2 becomes metal without a band gap.[99] Moreover, Kis et al. lowering the melting points of precursors (metals and metal

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Figure 4. The band gap of PdSe2 and PtSe2. a) Calculated electronic structures of PdSe2. b) Band gaps of PdSe2 obtained from first-principles calculations
and the inset is band gaps extracted from the optical absorption spectra. Reproduced with permission.[94] Copyright 2017, American Chemical Society.
c) Density-of-states (DOS) of the defect-free monolayer, bilayer, and trilayer PtSe2 by first-principles calculations. Reproduced with permission.[99]
Copyright 2018, Springer Nature.

oxides) and promoting a high mass flux by salt. The vapor can reach ≈5 × 105 µm2. Moreover, the vertical and lateral TMDs
pressure of the molten salt is much higher than many metal heterostructures based on m-TMDs can also be synthetized by
oxides. Here, NaCl-assisted CVD growth is taken as an example salt-assisted CVD method and we will discuss the heterostruc-
to illustrate the reaction route: tures based on m-TMDs in the following section.

NaCl + MOz → MOx Cl y +······ (1)

3.1.2. Controlled Growth of m-TMDs

MCl x Oy ( g ) + H2 ( g ) + X (S, Se , Te ) Layer Number Tuning: To our knowledge, a large number of lit-
(2)
→ MX 2 + HCl ( g ) + H2 O ( g ) + H2 X ( g ) erature has reported the transition of s-TMDs from indirect to
direct band gaps with the decrease of their thickness from bulk
to monolayer,[134,136] show great potential to enable exciting
The metal oxychlorides are formed by the reaction of metal new technological opportunities. Meantime, up to now,
oxides and salts, which evaporate at an appropriate tempera- m-TMDs have received widespread attention for their layer-
ture of 600–850 °C and promote the growth of the TMDs dependent fascinating properties such as CDW, superconduc-
(Figure 5b). The salt-assisted CVD method can be widely used tivity and magnetism, and potential applications in electronics,
to fabricate a large number of large-area single-layer m-TMDs spintronic devices, ultrafast memories, catalysis, and energy
such as 1T-TiSe2,[24] 2H-NbSe2,[77] and 3R-TaSe2[37] (Figure 5c–e). engineering.[137] There are a lot of achievements in controlling
As illustrated in Table 3, using the transition metal chloride as the thickness of m-TMDs especially for monolayer and few
the precursors, the m-TMDs synthetized by CVD are usually layers. For example, Kis et al. reported that as the thickness of
multilayers, owing to highly active of low-melting-point metal semimetallic 2D PtSe2 reduces from ≈13 to 2.5 nm, the transi-
chloride. While, using transition metal oxides and alkali hal- tion of metal-to-semiconductor occurs.[100] Liu et al. reported
ides as the precursors, the m-TMDs synthetized by salt-assisted that when the thickness of metallic 2D NbSe2 decreases from
CVD tend to have the characteristics of monolayer and large- 10-layer to monolayer, there is a change of SC transition tem-
area due to the slower metal-precursor feeding rate, which perature from 4.56 to 1.0 K.[77] In addition, NiTe2,[38] PtTe2,[35]
further promotes the production of millimetre-sized m-TMDs and CoTe2,[127] present tunable electrical properties related to
monolayer or the continuous m-TMDs films. For example, Liu their layer numbers. The thickness of the m-TMDs has a pro-
et al. reported that the lateral dimension of NbSe2 monolayer[77] found effect on their physical properties, therefore it is very
grown with NbOx and NaCl as precursors can reach 0.2 mm and urgent to define a reliable method to control the thickness of
large-area TiSe2 film[24] grown with TiOx and LiCl as precursors m-TMDs precisely.

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Table 3. Summary of CVD synthesis of 2D m-TMDs.

m-TMDs Sources materials Phase Morphology Thickness Temperature [°C] Substrate Carrier gas [sccm] Growth time [min]
TiS2 Ti + NH4Cl + S[101] 1T Nanosheet 0.6 nm 450 Mica 332.5Ar/17.5H2 10
TiSe2 TiOx + LiCl + Se[24] 1T Nanosheet/flim Monolayer 600 SiO2/Si 80Ar/15H2 13
TiCl4 + C8H18Se[102] 1T Thin flim 300 nm 600 Glass 100N2 1
TiTe2 TiO2 + NaCl + Te[53] 1T Nanosheet 5 nm 800–850 SiO2/Si 110Ar/20H2 10–15
ZrTe2 ZrO2 + NaCl + Te[53] 1T Nanosheet 2 nm 800–850 SiO2/Si 100Ar/20H2 10–15
HfTe2 Hf + NaCl + Te [53] 1T Nanosheet Few layers 800–850 SiO2/Si 120Ar/20H2 10–15
VS2 VCl3 + S[103] 1T Nanosheet 6.8 nm 600 SiO2/Si 100Ar/2–10H2 10
VCl3 + S[104] 1T Nanosheet / 550 SiO2/Si N2 with 10% of H2 10
VCl3 + S [105] 1T Nanosheet 7.6 nm 650 h-BN/SiO2/Si 80 Ar/20H2 20
VSe2 VCl3 + Se[106] 1T Nanosheet 4.9 nm 600 Mica 100Ar/2–10H2 10
VCl3 + Se[105] 1T Nanosheet 48.5 nm 650 h-BN/SiO2/Si 80Ar/20H2 20
VTe2 VCl3 + Te[39] 1T Nanosheet 8 nm 600 SiO2/Si 70Ar 10
VCl3 + Te[107] 1T Nanosheet 1 nm 600 WS2/WSe2 70Ar 10
VCl3 + Te[108] 1T Nanosheet 3.2 nm 610 Mica 80Ar/5H2 15
NbS2 Nb2O5 + NaCl + S[53] 2H Nanosheet 0.7 nm 750–850 SiO2/Si 80Ar/16H2 3–5
NbCl5 + S[109] 3R Nanosheet 20 nm 800 Graphene 200Ar 10
NbCl5 + S[36] 3R Nanosheet 0.7 nm 650 h-BN/SiO2/Si Ar/H2 /
NbCl5 + S[110] 3R Nanosheet 1.8 nm 1050 h-BN/sapphire 400Ar 10
NbSe2 NbOx(x≤ 2.5) + NaCl + Se[77] 2H Nanosheet 1.1 nm 795 SiO2/Si 120Ar/24H2 13
NbTe2 NbCl5 + Te[39] 1T Nanosheet 4.5 nm 580 SiO2/Si 200Ar/20H2 10
NbCl5 + Te[107] 1T Nanosheet 2.5 nm 540 SiO2/Si 60Ar/6H2 10
TaS2 TaCl5 + S[28] 1T Nanosheet 2 nm 820 SiO2/Si 90Ar/10H2 4
TaCl5 + S [111] 1T Nanosheet 18 nm 600 Nanoporous gold 100Ar/10H2 5
TaCl5 + NaCl + S[54] 1T Powder / 600 / 100Ar/10H2 5
TaCl5 + S[112] 1T Nanosheet 0.8 nm 850 h-BN 36Ar/4H2 1–4
TaCl5 + S[55] 2H Nanosheet 3 nm 750 Au foil 100Ar/10H2 10
TaSe2 TaCl5 + Se[113] 2H Nanosheet 0.8 nm 930 Au foils 100Ar/30H2 3
Ta/TaCl5 + Se[37] 3R Nanosheet 1.4 nm 800 SiO2/Si 32Ar/8H2 12
TaTe2 TaCl5 + Te[39] 1T′ Nanosheet 3 nm 620 SiO2/Si 30Ar/7H2 10
TaCl5 + Te[107] 1T′ Nanosheet 2.6 nm 610 SiO2/Si 30Ar/7H2 10
CrSe CrCl3 + Se[30] 1T Nanosheet 2.5 nm 735 Mica 100Ar/10H2 10
CrSe2 Cr-Au + Se[114] 1T Nanosheet / 850 Au 100Ar 10–15
CrCl3 + Se[31] 1T Nanosheet 0.7 nm 710 WSe2 120Ar/2H2 8
CrTe2 Cr-Au + Te[114] 1T Nanosheet / 850 Au 100Ar 10–15
CrCl2 + Te[115] 1T Nanosheet 1.2 nm 720 SiO2/Si 200Ar/1H2 2
Cr2Te3 CrCl3 + NaCl + Te[116] 1T Nanosheet 1.6 nm 850 Mica Ar/H2 /
[117]
MoS2 K2MoS4 1T′ Nanosheet 0.9 nm 750 Mica 90% Ar/10% H2 /
MoTe2 MoO3 + Te[118] 1T′ Nanosheet 2.1 nm 800 SiO2/Si 2 0Ar/10H2 10
MoO3/MoCl5 + Te[119] 1T′ Nanosheet Monolayer 780 SiO2/Si 200 Ar/15H2 5–15
Mo + Te[120] 1T′ Film / 650 SiO2 /Si 500 Ar/100H2 20
MoO3 + Te[121] 1T′ Film 0.725 nm 680 SiO2/Si Ar/H2 15
MoO3 + NaCl + Te[72] 1Td Nanosheet Monolayer 700 SiO2/Si 80Ar/15H2 4
WTe2 WO3/WCl6 + Te[119] 1T′ Nanosheet Monolayer 820 SiO2/Si 150 Ar/15H2 5–15
(NH4)2WO4 + Te[122] 1T′ Nanosheet 0.8 nm 650 SiO2/Si 350 N2/22H2 6
W + Te[123] 1Td Film 10 nm 800 SiO2/Si Ar/H2 50
FeSe Fe-Au + Se[114] 1T Nanosheet / 850 Au 100 Ar 10–15

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Table 3. Continued.

m-TMDs Sources materials Phase Morphology Thickness Temperature [°C] Substrate Carrier gas [sccm] Growth time [min]
FeTe FeCl2 + Te[88] Tetragonal Nanosheet 3.6 nm 530 SiO2/Si 100 Ar/10H2 10
FeCl2 + Te[88] Hexagonal Nanosheet 2.8 nm 590 SiO2/Si 100 Ar/10H2 10
FeCl2 + Te [124] Tetragonal Nanosheet 0.9 nm 600 SiO2/Si 45 Ar/5H2 1
FeCl2 + Te[124] Hexagonal Nanosheet 2.3 nm 750 SiO2/Si 45 Ar/5H2 10
FeTe2 FeCl3 + Te[125] Hexagonal Nanosheet 6 nm 720 Mica 220 Ar/20H2 15
CoS2 Co3O4 + NaCl + S [126] 1T Nanosheets Monolayer 740 MoSe2 45 Ar/5H2 3
Co3O4 + NaCl + S[126] 1T Nanosheets 7.2 nm 740 SiO2/Si 45 Ar/5H2 3
CoSe2 Co3O4 + NaCl + Se[126] 1T Nanosheet Monolayer 740 MoSe2 45 Ar/5H2 3
Co3O4 + NaCl + Se [126] 1T Nanosheet 5.1 nm 740 SiO2/Si 45 Ar/5H2 3
CoSe CoCl2 + Se[89] Tetragonal Nanosheet 2.3 nm 540 SiO2/Si 44 Ar/4H2 15
CoCl2 + Se[89] Hexagonal Nanosheet 3.7 nm 600 SiO2/Si 44 Ar/2H2 15
CoTe2 Co3O4 + NaCl + Te[126] 1T Nanosheet Monolayer 740 MoSe2 45Ar/5H2 3
Co3O4 + NaCl + Te[126] 1T Nanosheet 3.9 nm 740 SiO2/Si 45Ar/5H2 3
CoCl2 + Te [127] 1T Nanosheet 3.1 nm 580 SiO2/Si 63 Ar/7H2 15
NiS NiCl2 + S[128] 1T Nanosheet 2 nm 520 SiO2/Si 100 Ar/2H2 10
NiS2 NiCl2 + S[128] 1T Nanosheet 7 nm 520 SiO2/Si 100 Ar/2H2 10
NiSe NiCl2 + Se[129] 1T Nanosheet 6.5 nm 570 SiO2/Si 50 Ar/1H2 15
NiCl2 + Se[129] 1T Nanosheet 0.8 nm 540 WSe2 60 Ar/3H2 15
NiTe2 NiCl2 + Te[38] 1T Nanosheet 0.9 nm 530 SiO2/Si 60 Ar/5H2 15
NiCl2 + Te[130] 1T Nanosheet 3.1 nm 595 Mica 150 Ar/15H2 –
NiCl2 + Te[131] 1T Nanosheet 5.2 nm 550 MoS2 57 Ar/3H2 15
PtSe2 PtCl2 + Se[132] 1T Nanosheet 0.8 nm 800 Au foils 85 Ar/15H2 10
H2PtCl6 + Se [133] 1T Nanosheet 3.5–10 nm 900 Sapphire 100 Ar/10H2 30
PtTe2 Pt + Te[35] 1T Nanosheet 1.8 nm 1100 SiO2/Si 120 Ar 30
NaCl + PtCl4 + Te[134] 1T Nanosheet 4.2 nm 800 Mica Ar 30

First, the layer numbers of the 2D m-TMDs could be reg- with the evolution of the layer numbers of ultrathin NbS2,[138]
ulated by adjusting the growth temperature. In Figure 6a, as VTe2,[39] NbTe2,[39] TaTe2,[39] PtTe2,[35] CoTe2[127] single crystals,
the growth temperature decreases from 650 to 530 °C, the and so on. Third, the growth substrates (SiO2/Si, mica, and lay-
layer numbers of NiTe2 nanosheets reduce from ≈13–17 to ≈1–2 ered 2D materials without dangling bonds, such as graphene,
layers.[38] At lower growth temperatures, the growth of NiTe2 h-BN, and TMDs.) also have significantly influences on the
nanosheets is mainly controlled by kinetics. So, the nuclea- thickness of 2D m-TMDs. In Figure 6c, the thickness of NbTe2
tion rate of the source atoms is relatively high, and they quickly nanosheets grown on 2D WSe2 substrate is thinner than that
join the fastest growth front based on edge energetics, thereby on SiO2/Si.[107] The WSe2 nanosheet is beneficial to the lateral
constructing the nanosheets thinner. In comparison, at higher growth of NbTe2 nanosheets owing to their homogeneous sur-
growth temperatures, the growth of NiTe2 nanosheets is largely face with low surface energy and few defects, which promotes
controlled by thermodynamics, resulting in a lower nuclea- the growth of thiner NbTe2 single crystals. This method also
tion rate to obtain thicker nanosheets. Similarly, by decreasing has been applied to reduce the thickness of VTe2,[107] TaTe2,[107]
the growth temperature, layer numbers of other m-TMDs NbS2,[109] and NiSe[129] nanosheets. Moreover, the decreasing of
such as PtTe2,[35] CoTe2,[127] and NiSe[129] single crystals acquire thickness of the other 2D m-TMDs such as MoTe2, WTe2, and
controllable reduction. Second, the tunning of thickness of NbS2 can be obtained by reducing the growth time. In conclu-
the 2D m-TMDs could be obtained by modulating the flow sion, the thickness of m-TMDs can be precisely adjusted by
rate. In Figure 6b, as the flow rate of Ar increase from 100 to modulating the growth temperature, flow rate, substrate, and
500 sccm, the thicknesses of VSe2 nanosheets transform from growth time.
≈90 to ≈4.9 nm.[106] Under the experimental conditions of high Phase Control: In the previous literature, according to metal
flow rate condition, the growth of 2D m-TMDs is more kineti- and chalcogen atoms can be combined in different ways,
cally controlled rather than thermodynamically controlled. m-TMDs have a wide variety of phases (including 1T, 1T, 1Td, 2H,
Therefore, the thinner m-TMDs were synthesized, because the and 3R), which makes m-TMDs have different physical proper-
precursors can be quickly added to the most active growth front ties. Therefore, the precise phase control of m-TMDs is another
at the edge of the existing nanosheets, which is consistent vital topic for future research. So far, various properties have

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Figure 5. Salt-assisted CVD growth of 2D m-TMDs. a) The schematic mechanism of the salt-assisted CVD reactions. 1–3) The addition of salt reduces
the melting point of the precursor. 4) A comparation of the Nb nucleus with and without salt. 5–7) The production of oxychloride further promotes the
reaction process. b) The differential scanning calorimetry curves of the mixture of salts and metal sources. Reproduced with permission.[53] Copyright
2018, Springer Nature. The optical microscope (OM) images of the single-crystalline CVD-grown c) 1T-TiSe2 monolayers, d) 2H-NbSe2 monolayers, and
e) 3R-TaSe2 monolayers. c) Reproduced with permission.[24] Copyright 2018, Wiley-VCH, d) Reproduced with permission.[77] Copyright 2017, Springer
Nature. e) Reproduced with permission.[37] Copyright 2020, American Chemical Society.

been found in different phases of m-TMDs including quantum marize several strategies for overcoming energy barriers and
spin Hall effect in 1T′-TMDs,[139–141] Ising superconductivity achieving the stable phase and metastable phase of m-TMDs in
in monolayer 2H-TMDs,[142] nonlinear Hall effect, and asym- the CVD process.
metric spin-orbit coupling in few-layer 1Td-TMDs.[72] Moreover, First of all, the phase of TMDs can be precisely regulated by
the phase difference affects the electrical properties of TMDs, adjusting the growth temperature (TG) due to slight differences
for example, Suenaga et al. reported that 2H-MoS2 is semicon- in ground state energy between several phases. In Figure 7a,
ductor while 1T-MoS2 is metal.[143] So far, many methods have when the growth temperature is reduced from 710 to 670 °C,
been applied to realize the transformation between H phase the phase of few-layer MoTe2 transform from 1T′ to 2H.[71] But,
and T phase involving elemental doping,[144,145] heating,[34,143] at the middle growth temperature (670 ≤ TG ≤ 710 °C), 1T′/2H
laser irradiation,[33] chemical modifications,[146,147] electrostatic mixtures are produced with different ratios. The STEM images
gating,[148] and strain.[149] The CVD method can directly con- in Figure 7a show the zigzag array of Mo and Te atoms preferen-
trol the m-TMDs with different phases during the growth pro- tially along the [010] direction for 1T′-MoTe2 and the hexagonal
cess. Generally, for most TMDs, the thermodynamically stable array of alternate Mo and Te atoms. In addition, the 2H-MoTe2
phase is easy to form, while the metastable phase is difficult to nanosheets are semiconductor with band gap of ≈1.1 eV, and
acquire due to their higher formation energy. Herein, we sum- the 1T′-MoTe2 nanosheet is metal. Similarly, Zhai et al. reported

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Figure 6. The tunable layer numbers of m-TMDs. a) The change of the thickness of NiTe2 nanosheets with increasing temperature. Reproduced with
permission.[38] Copyright 2018, American Chemical Society. b) The evolution of average thickness of VSe2 nanosheets with increasing Ar flow rate.
Reproduced with permission.[106] Copyright 2017, Wiley-VCH. c) The OM images and corresponding thickness distribution of the NbTe2 nanosheets
grown on the WSe2 and SiO2/Si substrate. Reproduced with permission.[107] Copyright 2019, Wiley-VCH.

the transformation from 1T′-MoTe2 to 3R-MoTe2 by decreasing evolution from layered tetragonal FeTe single crystal to nonlay-
the deposition temperature;[150] Duan et al. reported that as the ered hexagonal FeTe single crystal by precisely increasing the
growth temperature increases, the evolution from 2D layered growth temperature.[88,124] In Figure 7b, Bartels et al. reported
tetragonal CoSe single crystal to nonlayered hexagonal CoSe the evolution from 1T-MoTe2 to 1T′-MoTe2 to 2H-MoTe2 few-
single crystal occurs.[89] Liu et al. and Gong et al. presented the layer films by reducing the growth quench temperature.[121]

Figure 7. The phase control of m-TMDs. a) Schematic illustration of the phase evolution and the STEM images of 2H-MoTe2 and 1T′-MoTe2 at the dif-
ferent growth temperature, respectively. Reproduced with permission.[71] Copyright 2017, Springer Nature. b) Schematic illustration of phase-selective
synthesis of 2H, 1T′, and 1T-MoTe2 few-layer films at the different quench temperature. Reproduced with permission.[121] Copyright 2017, American
Chemical Society. c) Schematic illustration of phase evolution and the STEM images of T′-KxMoS2 and 2H-KxMoS2 by adjusting K concentration. Repro-
duced with permission.[117] Copyright 2018, Springer Nature. d) Schematic illustration of the phase evolution of Td, 1T′, and 2H Se-substituted MoTe2
films by controlling the Se concentration. Reproduced with permission.[151] Copyright 2019, Wiley-VCH.

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Once the clam shell is opened, the process tube will be directly
cooled by the fan. When clam shell is opened at 450 °C, the
1T-MoTe2 is dominantly attained. When clam shell is opened
at 350 °C, the 1T′-MoTe2 phase is dominantly acquired. Finally,
if the clam shell is opened below 100 °C, the 2H-MoTe2 phase
is dominantly obtained. The 1T-MoTe2 nanosheets are obtained
at high cooling temperature of ≈450 °C, because the growth is
quenched rapidly enough when the cooling progress starting
at sufficiently high temperatures. Decreasing the cooling
temperature to ≈350 °C, the 1T′ phase is thermodynamically
stable, and it will be obtained. When the cooling temperature
further decreases to <100 °C, the 2H-MoTe2 nanosheets can be
obtained because the 2H phase is a thermodynamically stable
phase near room temperature. In short, the phase at each tem-
perature is the thermodynamically preferred one. Furthermore,
in Figure 7c, 1T′-KxMoS2 and 2H-KxMoS2 can be converted each
other via tuning the concentration of K under a reductive atmos-
phere. When K concentration is less than 44%, the 2H-MoS2
is produced in the Ar atmosphere, owing to the significantly
higher formation energy of the 1T′ phase than that of the 2H
phase. As the concentration of K exceeds 44%, the 1T′-MoS2
monolayer is obtained in a mixture of H2 and Ar atmosphere
because the 1T′-KxMoS2 is more stable than the 2H-KxMoS2.[117]
Lastly, Figure 7d shows the phase transition from Td, to 1T′ and
2H in Se-substituted MoTe2 thin films by increasing the Se
concentration.[151] Moreover, Lee et al. reported the phase transi-
tion from 1T′-MoTe2 to 2H-MoTe2 by prolonging growth time
under the Te atmosphere.[120] In summary, the phase evolution
of TMDs can be obtained by accurately controlling the growth
temperature, cooling temperature, formation energy, element
doping, and growth time in the CVD process. Figure 8. The precise lateral sizes and orientation control. a) The OM
image of NbSe2 monolayer with lateral dimension of 200 µm. Repro-
Lateral Sizes and Orientation: Compared with small-scale duced with permission.[77] Copyright 2017, Springer Nature. b) The OM
single crystals or large-sized polycrystalline films, the single image of NiTe2 on mica. Reproduced with permission.[130] Copyright 2020,
crystals of 2D m-TMDs with wafer-scale sizes can provide American Chemical Society. c) Schematic diagram of NiSe on WSe2 exhib-
more fundamental physical phenomena or related more prac- iting the relative lattice orientations. d) The OM image of NiSe on WSe2.
tical applications. Therefore, it is imperative to find an effective Reproduced with permission.[129] Copyright 2019, Springer Nature. e) The
method to prepare large-size 2D m-TMDs single crystals. The OM image of VSe2 arrays on WSe2 monolayer. Reproduced with permis-
sion.[154] Copyright 2020, Springer Nature.
m-TMDs can grow from a nucleus to form a large-scale single
crystal by adjusting the growth parameters. For example, the
1T′-WTe2 monolayer[119] with lateral dimension of ≈350 µm and large single crystals m-TMDs films by elongating the growth
2H-NbSe2 monolayer with a lateral domain size of ≈200 µm time. Recently, researchers have found that substrates play a
(Figure 8a)[77] can be synthesized on SiO2 substrates by the critical role in the controlling of the crystal lattice orientation
salt-assisted CVD method. And the single-crystalline few-layers during the growth of 2D m-TMDs. The orientation preference
1T-NiTe2 with a large domain size of ≈1.5 mm can be produced of m-TMDs is mainly determined by the strong van der Waals
by prolonging the growth temperature and time.[130] But, com- (vdW) interaction and the degree of lattice matching between
pared to s-TMDs grown by CVD, the size of m-TMDs grown by the substrate and the m-TMDs. Mica (KMg3(AlSi3O10)F2)
CVD is still far small. This strategy of growing from a nucleus is more conducive to control the orientation of m-TMDs owing
to form an ultrathin large-scale single-crystalline has very high to its layered structure, smooth surface without a dangling
requirements for the controlling of growth parameters, and it is bond, and compatibility with vdW epitaxy. For example, the as-
difficult to obtain large single crystals above centimeters. grown NiTe2 on the mica clearly shows well-aligned hexagonal
It is of great significance to control the orientation of well- or triangular shapes (Figure 8b).[130]
aligned m-TMDs array for preparing wafer-scale single crystal In addition, 2D materials (graphene, h-BN, and TMDs) are
m-TMDs ultrathin films. Moreover, the uniformity and perfor- very effectively used as the substrate for controlling orientation
mance of 2D m-TMDs devices can be significantly enhanced by of m-TMDs owing to their high-quality single crystal, atomic
fabricating wafer-scale single-crystalline 2D m-TMDs with few flat surface, and lattice symmetry. In Figure 8c, when NiSe
grain boundaries. Inspired by the aligned growth of large single nanosheets are epitaxially grown on WSe2 substrate, it exhibits
crystals of graphene films,[152,153] it is feasible to combine the the relative edge orientations with 0° and 60°,[129] and the cor-
parallel m-TMDs arrays (triangular single-crystal with a 120° responding OM image of grown NiSe nanosheets on 2D WSe2
rotation and hexagonal single-crystal with a 60° rotation) to form are shown in Figure 8d. The as-grown NbS2 on top of h-BN

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clearly reveals well-aligned hexagonal or triangular shapes.[110] the mixture of 2H and 1Td to 1Td.[161] Liu et al. presented that the
Similarly, other m-TMDs such as VTe2, NbTe2, and TaTe2 single increase of doping W can induce a semiconductor-to-metallic
crystals show well-aligned orientation with the WSe2 and WS2 transition in Sn1−xWxS2, and at the x = 100% limit, products
substrates.[107] Furthermore, by selectively forming nucleation transform back to the semiconductor.[162] The CVD method
sites on WSe2 monolayer or bilayer, VSe2 arrays are obtained for elemental doping in TMDs is simple and scalable. Liu
on WSe2 (Figure 8e).[154] We can find that VSe2 single crystals et al. reported the strategy of Te-doped 1H-phase WS2 in that
are parallel to WSe2, which provides the possibility to grow with increase the chalcogen ratio from Te:S = 1:1 at H2 = 5 sccm
into large single crystals. But how to control the growth con- to Te:S = 10:1 at H2 = 15 sccm, the phase of WTe2S2(1−x) mono­
ditions to seamlessly grow parallel small single crystal arrays layer transforms from 1H to 1T′.[163] Similarly, this research
into wafer-scale single crystal m-TMDs remains to be further group also demonstrated the structural phase transition from
investigated. Td to 1T′ to 2H by increasing the Se concentration in Se-sub-
Defects and Doping: The defects are easily presented in the stituted MoTe2.[151] The band gap engineering and phase con-
2D crystalline structure owing to their ultrathin thickness. trol through element doping provide a new opportunity for the
Compare to graphene, 2D TMDs with the alternating X–M–X research of basic physical properties and applications in various
structure have more defects.[155,156] The major sources of fields including high-performance electronic and optoelectrical
defects are atomic vacancies in 2D TMDs including chalcogen devices, catalysis, energy storage, and so on.
vacancies, metal vacancies, or both of them. Usually, atomic
vacancies are inevitably generated and seriously degrade the
crystalline quality and physical properties such as charge car- 3.1.3. 2D m-TMDs/s-TMDs Vertical Heterostructures
rier mobility.[157] Moreover, a number of different defects in
TMDs can significantly alter their physico-chemical properties. Combinations of TMDs with different compositions into vdW
For example, the existence of a line of S vacancies converts the heterostructures (vdWHs) have become research hotspot in
semiconducting MoS2 into metallic MoS2 by theoretical calcu- recent years, providing a new way for the design and prepa-
lations.[158] The effectively control in the generation of atomic ration of novel materials with unique properties. The vdWHs
vacancies by the post chemical or physical processes (laser provide a reliable platform for studying new interlayer cou-
irradiation, electron beam irradiation, plasma treatment, or pling between different materials and offer multiple physical
annealing process) in the 2D m-TMDs can be used in energy properties to satisfy different application requirements.[164,165]
storage, catalysis and conversion, sensors, and other fields.[159] Vertical vdWHs are stacked layer by layer vertically with weak
For instance, Te vacancies could be introduced by laser irra- vdW interlayer interaction between the different layers without
diation in few-layer MoTe2, and phase transition from the 2H requirement for lattice matching between them and beyond the
to 1T′ phases was observed.[33] Defects could be introduced in processing compatibility requirements in conventional bonded
1T-TaS2 via the oxygen plasma, which served as the catalytic heterosturctures. Up to now, despite intense interest has been
active sites to enhance hydrogen evolution reaction (HER).[160] put in and considerable progress have been achieved, most of
These vacancy/defect-introduced approaches are universal and the vertical vdWHs have been produced via mechanical exfo-
promising property-tuning strategies in defect engineering of liation and manual re-restacking method.[166,167] For example,
TMDs. Meanwhile, CVD is an effective method to control the the NbS2 and MoS2 nanosheet produced by mechanical exfolia-
formation of atomic vacancies, for example, by adjusting the tion were superimposed on each other to form heterostructure
flow of sulfur vapor, the concentration of S vacancies in WS2 Schottky diodes. However, this method has the disadvantage of
and MoS2 monolayer can be effectively controlled.[159] But the low yield and poor reproducibility, which is obviously cannot
controlled synthesis of atomic vacancies for m-TMDs is still be applied to practical technologies.[168] In recently, Nb2O5 and
particularly scarce. WO3 were directly selenized at high temperature via a CVD
In addition to the above-mentioned defects control, ele- method followed by a layer-by-layer stacking technique to pro-
mental doping is another strategy for adjusting the physical duce NbSe2/NbxW1−xSe2 vertical vdWH, which is tedious and
properties of 2D m-TMDs. For example, the phase transition incompatible.[169] It is necessary to broaden the method for
from Td to 1T′ below 200 K could be found in 2D MoTe2 via preparing vdWHs with reliability, scalability, uniformity, and
intrinsic electron doping.[86] If the dopant is well matched with reproducibility. The CVD method exhibits superior flexibility
the TMDs nanosheets in terms of electronegativity, atomic and controllability for the rational growth of high-quality het-
valence, coordination, and size, the dopant atoms can be added erostructures, which is a critical step to explore new scientific
to the crystal lattice of the m-TMDs nanosheets by replacing lat- phenomena. However, there are only a few vertical vdWHs that
tice atoms, otherwise, the dopant atoms will squeeze intersti- have been prepared using CVD method to date, and nearly all
tial structure of the lattice.[137] It is important that the doping of them have been focused on s-TMDs/s-TMDs vdWHs,[170–173]
concentration should be lower than a certain ratio to assure and it remains a huge challenge to direct integrate the high-
that the dopant does not change the intrinsic crystal structure quality m-TMDs/s-TMDs vdWHs with a clean interface. The
of the host material. Specifically, the doping method has been reason for the relatively few CVD synthesis m-TMDs/s-TMDs
demonstrated for band gap engineering and phase control of heterostructures is the following two points: I) compare to
TMDs materials to change their physical and chemical prop- s-TMDs/s-TMDs vdWHs with the same crystal structure such
erties. Liu et al. demonstrated that as doped Te concentration as 2H-WS2 and 2H-MoS2, it is hard to obtain the m-TMDs/s-
increase from x = 0–0.4 to x = 0.5–0.6 to x = 0.7–1.0, the phase TMDs vdWHs with different crystal structures such as 1T and
of WSe2(1 − x)Te2x monolayer can be precisely tuned from 2H to 2H, these two components should be carefully selected for

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Figure 9. Schematic of the CVD synthetic strategy of m-TMDs/s-TMDs vertical vdWHs. a–d) Schematic illustration for synthesis of VSe2/WSe2 vertical
vdWH by the two-step CVD method and corresponding OM images of VSe2/WSe2 vertical vdWH at different stages. Reproduced with permission.[174]
Copyright 2019, American Chemical Society. e–i) Proposed mechanism of one-step CVD synthetic route for the NbS2/MoS2 vertical vdWH and OM
images of NbS2/MoS2 vertical vdWH at different stages. Scale bar: 10 µm. Reproduced with permission.[138] Copyright 2018, American Chemical Society.

epitaxial growth. II) Metal oxide precursors with high melting method (Figure 9a–d). First, the WSe2 monolayer was synthe-
points and low chemical reactivity make the synthesis of sized on the Al2O3 substrate. Subsequently, metallic 1T-VSe2
m-TMDs/s-TMDs vdWHs very difficult. multilayer prefers to nucleate and grow from the edge sites
To solve the above problems, the CVD method with of s-TMDs or other defective sites. Finally, a fully stacked ver-
reducing precursor temperature was also employed to grow tical VSe2/WSe2 vdWH is obtained by further prolonging the
m-TMDs/s-TMDs vdWHs directly, which can be divided into growth time. Based on the theoretical calculation, the edge-
two parts: two-step CVD method and one-step CVD method. elongated stack of VSe2/MX2 vdWH can be formed because the
For two-step CVD growth of VSe2/MX2 (M = Mo, W; X = S, edge sites of semiconducting MX2 monolayer are favorable to
Se) vertical vdWHs, the VCl3 was selected as a precursor can nucleation and growth of metallic VSe2 at the initial growth
effectively reduce the damage of the template material stage. Furthermore, Duan et al. successfully synthesized the
(s-TMDs) during the second growth, which is attributed to its m-TMDs (VTe2, NbTe2, TaTe2, and NiSe)/s-TMDs (WSe2 and
growth temperature (500–600 °C) is lower than or equal to the WS2) vertical vdWHs with chloride as precursor by two-step
degradation temperature of s-TMDs.[174] This can facilitate the CVD growth.[39,129] On the other hand, high-quality NbS2/MoS2
formation of clean vdW interfaces. Zhang et al. reported that vertical vdWH with a sharp atomic metal/semiconductor inter-
the preparation of VSe2/WSe2 vertical vdWHs by two-step CVD face can be obtained by one-step salt-assisted CVD method.[138]

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Figure 10. VSe2/WSe2 vertical vdWH arrays. a) Schematic illustration of the formation of m-TMDs/s-TMDs vertical vdWHs arrays by laser-patterning
and CVD method. b) The AFM image of a 3 × 3 VSe2/WSe2 vdWHs array. c) The cross-sectional STEM image and corresponding EDS mapping of VSe2/
WSe2 vdWH. d) Large-scale VSe2/MoS2 arrays. Reproduced with permission.[154] Copyright 2020, Springer Nature.

In Figure 9e–i, first, MoS2 grows and forms a monolayer single- the corresponding atomic force microscope (AFM) is shown in
crystal triangle owing to the lower temperature (650–750 °C) Figure 10b. The STEM images clearly revealed atomically sharp
of MoS2 nucleates. Second, as the temperature increases and nearly ideal vdW interfaces and well-defined Moiré superla-
to 800 °C, the metallic NbS2 prefers to nucleate and grow at ttices and widely tunable Moiré periodicity in multilayer-VSe2/
the corners with rich defects. Lastly, the NbS2 merges at the bilayer-WSe2 vdWH. (Figure 10c). In particular, more large
edge leading to the full coverage of the bottom MoS2. The 2D periodic arrays of VSe2/MoS2 vdWHs (>12 000 separated VSe2/
m-TMDs/s-TMDs vdWHs with the atomically sharp interface MoS2) can be readily achieved with a yield up to about 99% on
provide platforms for further exploring the 2D Schottky barrier highly oriented continuous MoS2 monolayer films (Figure 10d).
diodes or Ohmic contact in electronic devices. In short, these results confirm that this method has univer-
Duan’s group recently reported a general synthetic approach sality, controllability, and scalability for the growth of a wide
with precisely controlled nucleation and growth processes to range of 2D m-TMDs/s-TMDs vdWH arrays, and then can be
achieve 2D m-TMDs/s-TMDs vertical vdWHs arrays which are extended to more complex 2D vdWHs arrays including mag-
not limited to a material with specific chemical composition or netic and SC materials.
lattice structures.[154] In Figure 10a, for the VSe2/WSe2 vertical
vdWH array, the monolayer or bilayer WSe2 was first produced
by CVD methods, and then patterned periodic arrays of nuclea- 3.1.4. 2D m-TMDs/s-TMDs Lateral Heterostructures
tion sites could be obtained by laser patterning which allows the
creation of local defects at specific locations, avoids the contam- The direct deposition of the metal electrode on the 2D s-TMDs
ination of impurities, and thus minimizes undesired random causes the inevitable defects, disorder, strain, and metal dif-
nucleation in subsequent growth. Finally, the m-TMDs (such fusion at the interface, usually leading to serious Fermi-level
as VSe2) nucleate and grow on locations of pre-patterned WSe2 pinning and uncontrollable damage of underlying 2D s-TMD
defects to form m-TMDs/s-TMDs vertical vdWHs arrays and and Schottky barrier.[23,175,176] To solve this problem, the 2D

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Figure 11. Schematic of the CVD synthetic strategy of 2D m-TMDs/s-TMDs lateral heterostructures. a) Schematic diagram of the growth and corre-
sponding scanning electron microscope (SEM) image of 2D NbS2/WS2 lateral heterostructure. Reproduced with permission.[180] Copyright 2018, Wiley-
VCH. b) Schematic diagram of the growth and corresponding SEM image of 2D VS2-MoS2 lateral heterostructure. Reproduced with permission.[178]
Copyright 2018, American Chemical Society. c) Schematic diagram of the growth and corresponding OM images of the 1T′ m-MoTe2/2H s-MoTe2 lateral
heterostructure. Reproduced with permission.[181] Copyright 2019, American Chemical Society.

m-TMDs/s-TMDs vdWHs with atomically sharp dangling vdWHs, the CVD growth 2D m-TMDs/s-TMDs lateral het-
bond-free interfaces were produced to reduce Fermi level pin- erostructures is still scarce due to the chemical instability of
ning, effectively tune the Schottky barrier, and improve device m-TMDs, and the unknown surface/edge energetics of both,
electrical and optoelectronic properties. Lateral 2D m-TMDs/s- which can lead to in-phase alloying, coplanar stitching, and
TMDs heterostructures can also have opportunities to solve vertical stacking.[178,179] Moreover, to obtain ideal 2D m-TMDs/
this problem, which usually requires a relatively small lattice s-TMDs lateral heterostructures configurations by regulating
mismatch so that each component of the heterostructures can growth parameters, it is necessary to understand their growth
be stitched together in the same plane. Based on the phase mechanism.
transition from semiconductor to metal, a general approach The 2D NbS2-WS2 lateral heterostructure has been produced
for preparing 2D m-TMDs/s-TMDs lateral heterostructures by by two-step CVD growth (Figure 11a).[180] First, the WS2 mon-
converting part of the 2D s-TMD into 2D m-TMD is proposed. olayer was grown on the sapphire substrate by sulfurizing the
For example, 2D 1T′ m-MoTe2/2H s-MoTe2 lateral heterostruc- mixture of WO3 powder and NaCl powder. Then, NbS2 grew at
ture can be obtained by patterned laser irradiation with the the active growth front of WS2, resulting in 2D NbS2/WS2 lat-
phase transition from 2H to 1T′ in MoTe2 owing to the irre- eral heterostructure with a smooth surface. Figure 11b schemati-
versible Te vacancy.[33] The 1T-MoS2/2H s-MoS2 lateral hetero- cally shows the two possible growth mechanisms of the 2D VS2/
structure can be produced with the phase transition from 2H MoS2 lateral heterostructure. First, the VS2 nanosheets were
to 1T in MoS2 by organolithium chemical treatment.[146] And grown on the SiO2/Si substrate, and then, the growth of MoS2
the 2D 1T m-MoS2/2H s-MoS2 lateral heterostructure can be is guided by the edge or the surface of VS2. Finally, The MoS2
synthesized by Ar-plasma treatment, in which the phase tran- nanosheets grow outward along and surround VS2 to form the
sition occurs from 2H to 1T in MoS2 due to the sliding of VS2/MoS2 lateral heterostructure.[178] The large-scale coplanar
the top S-layer.[177] Beyond above method, CVD method with 2D 1T′ m-MoTe2/2H s-MoTe2 lateral heterostructure arrays
high degree of synthetic control opens up a new way to grow have been obtained based on the phase transformation from
high-quality 2D m-TMDs/s-TMDs lateral heterostructures 1T′ MoTe2 to 2H-MoTe2 (Figure 11c).[181] First, the large-scale
directly. Compared to the CVD growth of 2D m-TMDs/s-TMDs 2H-MoTe2 film was obtained on SiO2/Si substrate. Subsequently,

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the 2H-MoTe2/Mo film was prepared into stripes by photolithog- such as Te, Sn, Bi, and NaCl with low melting point and high
raphy, reactive ion etching, and magnetron sputtering (Mo depo- boiling point could decrease the reaction temperature and avoid
sition), followed by a lift-off process. Finally, the 2H-MoTe2/Mo vaporization during the reaction. For instance, 1T′-MoTe2 single
film was tellurized at a lower temperature (530 °C) for 30 min crystals could be attained via NaCl-flux with well-ground mixed
to form 1T′-MoTe2, while the 2H-MoTe2 would not be affected Mo and Te powders in an alumina tube.[34] The ultrathin single
after the second CVD growth. In addition, 2D 1T′ m-MoTe2/2H crystals of m-TMDs were then obtained by mechanical exfolia-
s-MoTe2 lateral heterostructure can be formed by controlling tion. However, the size and the number of layers of the exfoli-
growth temperature, in the progress, 2D 1T′ m-MoTe2 and 2H ated flakes are really difficult to control, which is obviously not
s-MoTe2 were formed at higher growth temperature (710 °C) and a practical application of scalability. To achieve the mass fabrica-
lower growth temperature (670 °C), respectively.[71] tion accommodated to the commercial applications, the mechan-
ical exfoliation method still faces huge challenge.

3.2. Other Synthetic Methods

3.2.2. Chemical Exfoliation
We will discuss several other synthesis methods for 2D m-TMDs
(Table 4) including: I) mechanical exfoliation, II) chemical exfo- The chemical exfoliation route is one of the top-down
liation, III) MBE, IV) hydrothermal method, V) salt-templating approaches to produce m-TMDs. The chemical intercalation is
synthesis, VI) topochemical transformation, and VII) phase often used to separate the adjacent layers, and the monolayer
transition from semiconductor to metal by post-treatments. or few-layer nanosheets and films are acquired through fur-
ther liquid exfoliation. As shown in Figure 12d, first, external
ions or molecules were inserted into the vdW gaps of m-TMDs
3.2.1. Mechanical Exfoliation to reduce interlayer forces of neighboring layers, causing the
interlayer expansion. But the interlayer expansion is often small
Since the method of mechanical exfoliation was first used to and less than 10%. And then, with the help of external mechan-
obtain graphene by Novoselov and Geim in 2004,[233] it promoted ical driving forces such as shearing, sonication, and milling,
the development of 2D materials and rapidly becomes one of the the layered bulks were separated into ultrathin nanosheets.[236]
most widely applied approaches. The ultrathin nanosheets were Despite the formation of uniform dispersion, these methods
obtained from the bulk crystals by mechanical force using scotch are difficult to form large-sized nanosheets due to the high
tape. The single- or few-layer 2D materials by simple mechan- energy drive input. For example, the sizes of TaS2, NbSe2,
ical cleavage exfoliation are intrinsic cleanliness, high-quality and TiS2 nanosheets produced by the chemical exfoliation
crystalline, and with extraordinary electrical properties,[234,235] approach are ≈1 µm.[237] It is still a huge challenge to increase
which are suitable for the fundamental studies. The bulk single the interlayer expansion force and obtain large-size and high-
crystals were synthesized through the chemical vapor transport quality TMDs. To solve this problem, Xie et al. reported that
(CVT) method and the self-flux method. The typical CVT growth the lager lateral dimension and high-quality m-TMDs mon-
of crystals is illustrated in Figure 12a.[234] The halogen elements olayers could be efficiently prepared by single-crystal exfolia-
and their compounds (such as I2, Br2, and AgCl) were used as tion method and followed by manual shaking within several
transport agents. In this process, with the assistance of trans- seconds (Figure 12e). Especially, the lateral dimension of TaS2
port agents, the raw materials were transported from the source monolayers with high crystalline quality could reach or exceed
region (high temperature) to the growth region (low tempera- 100 µm, while the initial crystal structure was still maintained
ture) to form single crystals. After the growth of m-TMDs bulk using the above method.[45] In addition, the phase transition
single crystals, a series of high-quality m-TMDs nanosheets such from semiconductor to metal occurs during the chemical inter-
as 2D MoTe2,[213] TaS2,[200] and WTe2[216] were obtained by fol- calation process. For example, a phase transition occurs in
lowed mechanical exfoliation (see Table 4). Intriguingly, one-step the MoS2 monolayer from semiconductor to metal by n-butyl
CVT growth for ultrathin m-TMDs nanosheets was also pro- lithium treatment.[146] Although the chemical intercalation and
posed by adjusting the reaction conditions and growth kinetics. exfoliation methods have the advantage of high-yield produc-
For example, the layer-controlled PtSe2[230] atomic crystals were tion and low cost, great efforts still should have been made to
synthesized by controlling the amounts of reactants and trans- avoid the undesirable phase transition defects and chemical
port agent (KCl) that can significantly reduce the transport rate in decomposition in the process.
the CVT process, as illustrated in Figure 12b. Similarly, ultrathin
highly crystalline 1T-TiSe2[183] nanosheets were obtained by accu-
rately regulating the mass transport during the CVT growth. In 3.2.3. Molecular Beam Epitaxy
Figure 12c, the flux method was general for forming m-TMDs
crystals by liquefying raw materials in solvent flux at high tem- Since the 1990s, MBE was first developed as an excellent way
peratures.[58] The crucible required in this process needs to meet to grow TMDs,[58] a large number of 2D m-TMDs could be suc-
the following two points: I) inertness that does not react with cessfully prepared by the MBE method in an ultrahigh vacuum
reactants; II) high-temperature tolerance. The raw materials and of 10−12 Torr, as shown in Figure 12g.[197] Therefore, the quality
flux materials are liquefied at high temperatures, and then the and crystallinity film produced by this method is extremely
solute is slowly solidified, crystallized, and precipitated out into higher than that produced by other synthetic methods, which
a single crystal during the cooling process. The flux materials is very beneficial for studying the intrinsic physical properties

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Table 4. Summary of other synthesis methods for m-TMDs (chemical vapor transport: CVT; mechanical exfoliation: ME; molecular beam epitaxy:
MBE; E-beam evaporation: EBE).

m-TMDs Synthesis method Substrate Phase Morphology Thickness Electronic characteristics

TiSe2 CVT[44] / 1T Single crystals / Metal
CVT + ME[182] C-plane sapphire 1T Nanosheet 4.8 nm Metal
[183]
MBE Bilayer graphene 1T Nanosheet Monolayer Semimetal
TiTe2 CVT[184,185] / 1T Single crystals / Metal
EBE[186] Bilayer graphene 1T Flim Monolayer Metal
ZrTe2 MBE[187] InAs(111) 1T Thin flim Monolayer Semimetal
HfTe2 MBE[188] AlN(0001) 1T Thin flim Few-layer Semimetal
VS2 Hydrothermal method[189] / 1T Nanosheet 2.488 nm Metal
Hydrothermal method[49] / 1T Nanosheet 1.51nm Metal
[190]
Liquid exfoliation / 1T Nanosheet 1.2 nm Metal
Liquid exfoliation[191] / 1T Nanosheet / Metal
V5S8 Salt-templating synthesis[51] NaCl 1T Nanosheet / Metal
VSe2 E-beam evaporation[192] HOPG 1T Flim Monolayer Metal
[50]
One-pot colloidal route / 1T Nanosheet 0.4 nm Metal
Liquid exfoliation[193] / 1T Nanosheet 2.28 nm Metal
Hydrothermal method[194] / 1T Cuboids / Metal
VTe2 CVT[195] / 1T Single crystals / Metal
NbS2 CVT[196] / 2H Single crystals / Metal
Salt-templating synthesis[51] NaCl 1T Nanosheet / Metal
NbSe2 MBE[197] h-BN 2H Nanosheet 1.0 nm Metal
CVT + ME[198] / 2H Single crystals / Metal
MBE[199] Bilayer graphene 2H Nanosheet / Metal
TaS2 Liquid exfoliation[45] / 1T Nanosheet 0.85 nm Metal
[46]
CVT / 2H Nanosheet 0.9 nm Metal
CVT + ME[200] / 1T Nanosheet 9.4 nm Metal
Chemical exfoliation[201] / 2H Nanosheet 1.1 nm Metal
CVT[202] / 1T Single crystals / Metal
Salt-templating synthesis[51] NaCl 1T Nanosheet 38 nm Metal
TaSe2 ME[203] / 2H Film 17 nm Metal
CVT + ME[204] / 2H Single crystals / Metal
TaTe2 CVT[205] / 1T Single crystals / Metal
CrSe2 CVT[206] / 1T Single crystals / Metal
CrTe2 CVT + ME[207] / 1T Nanosheet 3 nm Metal
MoS2 Chemical exfoliation[208] / 1T Nanosheet 1–5 µm Metal
Chemical interaction[209] / 1T′ Nanosheet Monolayer Metal
MoSe2 Hydrothermal method[210] / 1T Nanosheet / Metal
MoTe2 CVT + ME[211] / 1T′ Single crystals / Metal
CVT[212] / 1Td Single crystals / Semimetal
CVT[69] / 1T′ Single crystals / Semimetal
ME[213] SiO2/Si 1T′ Nanosheet / Metal
ME[214] SiO2/Si 1T′ Nanosheet / Metal
Flux[34] / 1T′ Single crystals / Semimetal
Flux[215] / 1T′ Single crystals / Semimetal
WTe2 ME[216] SiO2/Si 1Td Nanosheet 11.2 nm Semimetal
Liquid exfoliation[73] Si/SiO2 1Td Nanosheets 2–7 layers Semimetal
CVT + ME[217] / 1Td Single crystals / Semimetal

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Table 4. Continued.

m-TMDs Synthesis method Substrate Phase Morphology Thickness Electronic characteristics

[218]
Flux / 1T′ Single crystals / Semimetal
MBE[219] Bilayer graphene 1T′ Nanosheet 1.21 nm Semimetal
MBE[220] Bilayer graphene 1T′ Nanosheet Monolayer Semimetal
[221]
FeSe Solution chemistry method / 1T Nanosheet / Metal
FeTe Solution chemistry method[221] / 1T Nanosheet / Metal
CoS Hydrothermal method[222] / 1T Nanowire / Metal
[223]
Hydrothermal method / 1T Nanoparticle
CoS2 Hydrothermal method[224] / 1T Nanosheet
CoSe2 Hydrothermal method[225] / 1T Nanosheet
[226]
NiS2 CVT / 1T Single crystals / Metal
NiSe Topochemical transformation[52] Ni foam / Nanosheet 1.25 nm Metal
NiSe2 Hydrothermal method[227] / 1T Nanosheets / Metal
Topochemical transformation[228] / / Nanosheets / Metal
PdTe2 Flux[229] / 1T Single crystals / Semimetal
PtSe2 ME[100] SiO2/Si 1T Nanosheet 2.5 nm Metal
CVT[230] Mica 1T Nanosheet 0.9 nm Semimetal
CVT[231] Mica 1T Nanosheet 1.55 nm Semimetal
MBE[232] Bilayer graphene 1T Film 0.59 nm Semimetal
PtTe2 Flux[98] / 1T Single crystals / Semimetal

of 2D m-TMDs such as superconductivity, CDW, and mag- strategy with potential industrial application prospects, which
netism. For example, PtSe2 with controllable layers synthesized is widely used in the synthesis of m-TMDs nanosheets. For
by MBE method shows high conductivity and intriguing Dirac example, taking selenium dioxide (SeO2), and sodium molyb-
semimetallic properties;[232] The single-layer TiSe2 obtained date (Na2MoO4) and ethylenediamine (NH2C2H4NH2) as the
by MBE method exhibits CDW phenomenon;[183] NbSe2 precursors, Sun et al. presented that 1T-MoSe2 nanosheets with
monolayer produced by MBE method demonstrates CDW the thickness of 5–10 nm could be synthesized by hydrothermal
phenomena and superconductivity.[197] Various insulating sub- method at 200 °C for 12 h, which presents excellent Li ion
strates are employed to grow m-TMDs in the MBE method. In storage capacity.[210] Using sodium metavanadate (NaVO3) and
Figure 12h,i, monolayer NbSe2 grows on the h-BN with a high SeO2 as the starting precursors, Behera et al. obtained 1T-VSe2
orientation by the MBE method.[197] Moreover, the high quality nanosheets by hydrothermal method at 200 °C for 24 h, which
PtSe2 thin films with controllable layer numbers from mono­ can be applied to the high-performance supercapacitor elec-
layer to 22 layers were obtained by MBE method on bilayer trodes.[194] In particular, the hydrothermal method was mainly
graphene substrates.[232] High quality VSe2 nanosheets with applied to prepare various non-layered m-TMDs including
controllable layer numbers from monolayer to 10 layers were NiSe2 nanosheets,[227] CoS nanowires,[222] CoS nanoparticles,[223]
also successfully prepared by the MBE method on highly ori- and CoSe2 nanosheets,[224,225] which are hard to be synthesized
ented pyrolytic graphite (HOPG) and MoS2 substrates.[192] How- by the top-down method. For the synthesis of m-TMDs, the
ever, due to the long growth time for MBE method and the high hydrothermal method has the advantages of simplicity, low
cost of the MBE equipment and the precursors, it is difficult to cost, high yield, and scalability. But, the hydrothermal method
conduct scalable 2D m-TMDs synthesis through MBE methods. is very sensitive to experimental conditions such as precursors,
solvent systems, surfactants, and temperatures.

3.2.4. Hydrothermal Method

3.2.5. Salt-Templating Synthesis
The hydrothermal method is a bottom–up synthesis method
using water as the reaction medium to obtain high-yield ultra- Various salts such as NaCl and Na2SO4 with high melting
thin 2D m-TMDs.[238] In Figure 13a, the reactants, water, and points and boiling points could remain stable in high tempera-
surfactants are mixed at room temperature and then placed ture and have the advantage of low price and superior solubility
in a sealed container. The temperature of the reaction system in water, so they could be widely used as templates to effectively
must be higher than the boiling point of the solvent, which can synthesize 2D materials.[240] In Figure 13b, the typical salt-tem-
promote the generation of high pressure and further improve plating synthesis process is that:[241] first, the salt is added to
the crystallinity of m-TMDs.[210,239] The hydrothermal synthesis the precursor solution to form a mixture, the mixed solution
method has been regarded as a convenient and reproducible is heated to a specific temperature along with vigorous stirring

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Figure 12. The other methods for synthesis of m-TMDs. a) Schematics illustration of two methods for preparing 2D m-TMDs with CVT. Top: con-
ventional CVT growth followed by mechanical exfoliation approach. Bottom: one-step direct CVT growth method. Reproduced with permission.[234]
Copyright 2017, Wiley-VCH. b) Schematics diagram of one-step CVT method for synthesizing of PtSe2 with controllable thickness. Reproduced with
permission.[230] Copyright 2019, Wiley-VCH. c) Schematics illustration of the flux method. Reproduced with permission.[58] Copyright 2018, American
Chemical Society. d) Schematic diagram of chemical exfoliation process. Reproduced with permission.[236] Copyright 2013, American Association for the
Advancement of Science. e) Schematics illustration of preparing m-TMDs monolayer by partial lithiation method and only manual shaking. Reproduced
with permission.[45] Copyright 2019, American Chemical Society. f) Electrostatic force microscopy phase image of MoS2 monolayer which part of the
transition from semiconductor to metal by n-butyl lithium treatment. Reproduced with permission.[146] Copyright 2014, Springer Nature. g) Schematic
presentation of the MBE setup. h) Structure model of the monolayer NbSe2 grown on h-BN by MBE method, where crystallographic orientation is
limited. i) AFM image of NbSe2 grown on h-BN by MBE method. Reproduced with permission.[197] Copyright 2016, AIP Publishing.

until the water has completely evaporated and crystals are pre- including TaS2, V5S8, and NbS2, in which NaCl microcrystals
cipitated. Subsequently, the 2D materials grow on the surface are used as substrate/template to guide the growth of m-TMDs.
of salt by calcination in a tube furnace under high temperature The 1T-TaS2 nanosheets are inclined to grow at the edges, cor-
and specific atmosphere. Finally, the salt can be removed and ners, and curved surfaces of NaCl crystals owing to abundant
the 2D materials can be obtained by washing out of the salt nucleation sites, and can be effectively applied to the HER.[51]
template with deionized water. The lateral size and thickness The salt-templating synthetic system opens up a new method
of 2D materials are mainly determined by the surface size of for the preparation of m-TMDs with high yield.
the salt and the concentration of the precursor solution. In the
past few years, this strategy has been applied on the synthesis
of metallic transition metal oxides.[242] For instance, Song et al. 3.2.6. Topochemical Transformation
obtained hexagonal-MoO3, MoO2, MnO, and hexagonal WO3
using salt-templating synthesis process.[243] In recent years, The nonlayered materials are connected in three dimensions by
this synthetic strategy can be extended to the preparation of chemical bonds to form bulk crystals. It is challenging to synthe-
m-TMDs nanosheets. In Figure 13c, Zhang et al. demonstrated size the few-layer or single-layer non-layered materials because
the universal and large-scale synthesis of high-quality m-TMDs the bonds of non-layered compounds are difficult to break and

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Figure 13. The other methods for synthesis of m-TMDs. a) Schematics illustration of the hydrothermal method and the corresponding SEM image for
1T-MoSe2 nanosheets. Reproduced with permission.[210] Copyright 2021, American Chemical Society. b) Schematics representation of salt-templating
synthesis. Reproduced with permission.[241] Copyright 2017, American Chemical Society. c) Schematics representation of salt-templating synthesis
and the corresponding AFM image for TaS2 nanosheets. Reproduced with permission.[51] Copyright 2019, American Chemical Society. d) Schematics
diagram of the topochemical transformation and the corresponding SEM image for NiSe nanosheets. Reproduced with permission.[52] Copyright 2018,
Wiley-VCH.

the internal driving force for 2D anisotropic growth is lacking.[242] by selenizing the ultrathin Ni(OH)2 nanosheets, which retained
The topochemical transformation is a very effective method to the original structure of Ni(OH)2 nanosheets.[52]
synthesize 2D nonlayered materials in which guest elements
are introduced into the host structure to obtain new materials
that retain the structure/morphology of host materials. As we 3.2.7. The Method of Phase Transition from Semiconductor to
all know, the topochemical transformation method is widely Metal by Post-Treatments
applied to the synthesis of 2D non-layered materials including
transition metal oxides,[244] carbides,[245,246] and nitrides.[247,248] The phase transition from semiconductor to metal is another
In recently, the topochemical transformation method opens effective strategy to produce 2D m-TMDs. So far, the fascinating
up a new way toward the growth of high-quality nonlayered approaches involve e-beam irradiation,[143] laser irradiation,[33]
m-TMDs including NiSe,[52] NiSe2,[228] Ni0.33Co0.67Se2,[249] argon plasma,[177] chemical modifications,[146,147,251] electrostatic
Ni0.89Co0.11Se2,[250] etc. In Figure 13d, Ho et al. reported the topo- gating,[148] strain,[149] and so on have been developed. Figure 14a
chemical transformation approach to synthesize the vertically shows the phase transition from semiconducting (2H) to
stacked 1.25 nm NiSe nanosheets. Taking the Ni foam as pre- metallic (1T) phases in MoS2 monolayer by e-beam irradia-
cursor, ultrathin 2D layered Ni(OH)2 nanosheets (0.96 nm) were tion.[143] First, the 2H-MoS2 turns into α-phase which is a pre-
first prepared by a self-limiting tunable acid etching method. cursor or an intermediate consisting of 3–4 constricted MoS2
And then, the non-layered NiSe nanosheets could be obtained zigzag chains. And then, a triangular 1T phase-MoS2 begins

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Figure 14. The method of phase transition from semiconductor to metal by post-treatments. a) The e-beam irradiation. Reproduced with permission.[143]
Copyright 2014, Springer Nature. b) The laser-irradiation. Reproduced with permission.[33] Copyright 2015, American Association for the Advancement of
Science. c) The plasma-treated. Reproduced with permission.[177] Copyright 2017, American Chemical Society. d) The n-BuLi intercalation. Reproduced
with permission.[251] Copyright 2015, American Chemical Society. e) The electrostatic gating. Reproduced with permission.[148] Copyright 2017, Springer
Nature. f) The mechanical strain. Reproduced with permission.[149] Copyright 2015, American Chemical Society.

to form owing to numerous atomic displacements and atomic intercalation also occurs in MoS2, MoSe2, and WS2. Figure 14e
plane gliding. The area of 1T phase-MoS2 is gradually expanded shows the phase transformation from semiconducting (2H)
to ≈8.47 nm2 by prolonging the time of electron-beam scanning. to metallic (1T′) phases in MoTe2 monolayer by electrostatic
In Figure 14b, the laser beam is focused on the desired area to gating, because the electron population in MoTe2 can be manip-
thin the thickness of 2H-MoTe2 to a few layers, and can cause ulated by the ionic liquid which covers the monolayer and
the phase transition from the 2H to 1T′ phase in MoTe2, which the electrodes.[148] Under an electrostatic bias, 2H-MoTe2 was
is attributed to the formation of the Te vacancy.[33] Figure 14c injected with excessive electrons, and because the 2H phase was
illustrates Ar-plasma treatment method was employed to acti- expected to carry more energy than the 1T′ phase with excessive
vate the 2H→1T phase transition in MoS2 monolayer, owing electrons, the transition from 2H phase to 1T′ phase in MoTe2
to the lateral sliding of the top S-layer induced by Ar ions (in monolayer happened. Figure 14f demonstrates that the phase
plasma) carrying certain kinetic energies.[177] Figure 14d shows transition temperature of MoTe2 from semiconducting (2H)
n-BuLi treatment can convert semiconducting 2H-WSe2 into to metallic (1T′) phases can be controlled by mechanical strain
metallic 1T-WSe2, because large alkali metal atoms like sodium due to the reduction of the activation energy barrier in the tran-
will introduce a large strain in the pristine lattice.[251] This phe- sition state and modulation of cohesive energy of each phase
nomenon of semiconductor-to-metal phase transition by Li in response to strain.[149] These techniques of phase transition

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from semiconductor to metal by post-treatments may broaden presents a clear hysteresis loop at 15 and 100 K, which indi-
the methods for synthesizing m-TMDs, which can be expected cates that 16 L CrSe2 nanosheet is FM with a coercivity (HC)
to practical applications. of 0.185 T. With the temperature increasing, the value for HC
reduces, and vanishes above TC = 110 K. Figure 15b shows the
RMCD measurement of monolayer CrSe2 without clear hyster-
4. Physical Properties of m-TMDs esis. But, the TC of monolayer CrSe2 can be determined by the
Arrott plot (Figure 15c). With increasing temperature, the linear
In recent years, m-TMDs have received progressively more intercept decreases and approaches zero when the TC = 65 K of
attention, because they have manifested a wealth of physical monolayer CrSe2 is reached. Figure 15d demonstrates RMCD
properties including magnetism, CDW order, and supercon- signals of the CrSe2 nanosheets at different thickness at 15 K.
ductivity. Therefore, in this section, we will briefly summarize With the layer number increases, the HC increases and satu-
the m-TMDs based on physical properties in a neutral manner. rates at 16 L or more (Figure 15f). In Figure 15e, as the layer
number of CrSe2 nanosheet increases from 1 to 16 L or more
layers, the TC is enhanced strongly from 65 to 110 K. Moreover,
4.1. Magnetism in 2D m-TMDs Liu et al. reported that with the thickness reduces from 32 to
5 nm, the Néel temperature of tetragonal FeTe with antiferro-
Recently, a large number of research on intrinsic ferromag- magnetism decreases from 70 to 45 K and with the thickness
netism (FM) in 2D materials has been reported, for instance, reduces from 30 to 4 nm, the TC of hexagonal FeTe with fer-
FM can be observed in monolayer semiconducting CrI3 and romagnetism decreases from 220 to 170 K.[88] Figure 15g,h dem-
bilayer semiconducting Cr2Ge2Te6 at low temperatures.[90,92] onstrate the OM images of Hall-bar devices of tetragonal and
Despite this progress, the exploration of intrinsic magnetism hexagonal FeTe nanoplates, respectively, which were covered by
based on 2D m-TMDs is still scarce. The magnetic order in h-BN nanosheets to prevent ambient degradation. In Figure 15i,
m-TMDs is an attractive property that provides a platform for there are clear decrease in longitudinal sheet resistance (RS) at
fundamental studies of spin behavior and opens up exciting ≈70, ≈50, and ≈45 K, when the thicknesses of tetragonal FeTe
opportunities in spintronics, sensors, magnetoelectric, and is 32, 19, and 5 nm, respectively, which indicates that a non-
magneto-optoelectronics.[27,90,92,192] The magnetic anisotropy magnetic to antiferromagnetic transition has occurred. In
of 2D m-TMDs with the reducing crystal symmetry break the Figure 15j, when the thickness of hexagonal FeTe is 30, 12, and
restriction of the Mermin–Wagner theorem in which the 2D 4 nm, the temperature of phase transition from para­magnetism
isotropic Heisenberg model forbids the magnetic order at finite to FM is ≈220, ≈215, and ≈170 K, respectively. Figure 15k pre-
temperatures.[90] Several approaches can induce magnetism in sents the Hall resistance (Rxy) related to the magnetic field
2D materials, such as adsorption, doping, vacancies, adatoms, of tetragonal FeTe (32 nm) and hexagonal FeTe (30 nm) at
domain boundaries, and edges. In theoretical or experimental 1.5 K, further confirming the ferromagnetism of hexagonal
research, some 2D m-TMDs have been proven to have intrinsic FeTe and the antiferromagnetism of tetragonal FeTe. The
magnetic ordering such as VS2, VTe2, CrSe, CrSe2, CrTe2, temperature-dependent anomalous Hall effect (AHE) of the
Cr2Te3, CoS2, CoSe2, and FeTe.[27,30,31,39,58,88,115,116,192] hexagonal FeTe in Figure 15l shows that with the increase of
The intrinsic magnetic ordering in the VX2 (X = S, Se, and Te) temperature from 1.5 to 220 K, the saturation moment and the
monolayer owing to strong electron coupling in the 3d1 odd-elec- HC gradually decreases, and beyond this temperature, AHE dis-
tronic configuration of V4+ is predicted based on density functional appears. Moreover, He et al. presented that as the thickness of
theory (DFT) calculation.[252] The integer magnetic moments of Cr2Te3 decreases from 40.3 to 5.5 nm (4 units cell), the TC is
monolayer VS2, VSe2, and VTe2 close to 1.0 μB are calculated by the enhanced strongly from 160 to 280 K, owing to the reconstruc-
generalized gradient approximation. According to theoretical cal- tion and change of lattice parameters in nonlayered Cr2Te3.[116]
culations, VS2, VSe2, and VTe2 monolayer were room-temperature
FM material with Curie temperatures (TC) up to 292, 472, and 553
K, respectively. Wu et al. experimentally proved that few layer VS2 4.2. Charge-Density-Wave Phase in 2D m-TMDs
is a room-temperature FM material.[190] However, the magnetism
of VSe2 nanosheets is controversial, and recent various works In recent years, the CDW order of m-TMDs has attracted
refuted that VSe2 is well known now to be not ferromagnetic.[253] increasing and intense scientific and technological interests
For example, King et al. revealed no signatures of a FM ordering owing to it′s a periodic modulation of the electron density
in VSe2 monolayer synthesized by MBE method on bilayer gra- and the crystal lattice.[27,113] Understanding the CDW order in
phene/SiC examined by both the electronic structure calculation 2D m-TMDs is essential to unravel the mechanism of uncon-
and X- ray magnetic circular dichroism (RMCD) measurement. ventional superconductivity in many layered materials. As
The magnetic hysteresis (M–H) curve measured by physical the dimensionality is reduced, the Peierls instabilities (owing
properties measurement system (PPMS) demonstrates that to Fermi surface nesting) and electron–phonon interactions
few-layered VTe2 obtained by the CVD method exhibits room- (owing to the reduction of dielectric screening) strengthen,
temperature ferromagnetism.[39] Furthermore, many m-TMD which is beneficial to enhance CDWs. 2D m-TMDs (TiX2,
exhibit thickness-dependent magnetic properties. For example, TaX2, NbX2, etc., X = dichalcogenides) are important members
Duan et al. synthesized air-stable CrSe2 grown on the WSe2 sub- of CDW materials. The high CDW phase transition tempera-
strate with thickness-dependent FM properties.[31] The RMCD tures (TCDW) make 2D m-TMDs (such as TiSe2, TaS2, and
measurement of 16-layer (16 L) CrSe2 nanosheet (Figure 15a) TaSe2) show great potential to enable exciting new technological

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Figure 15. Magnetic characterization of the 2D CrSe2 and FeTe. a) RMCD signals of the CrSe2 (16 L) at 15, 100, and 130 K. b) RMCD signals of the CrSe2
(1 L) at 15, 50, and 80 K. c) Arrott plots of the RMCD signals of the 1 L CrSe2. d) RMCD signals of the CrSe2 nanosheets at different thickness. e) Rela-
tionship between HC and the thickness of CrSe2. f) Relationship between TC and the thickness of CrSe2. Reproduced with permission.[31] Copyright 2021,
Springer Nature. g,h) OM images of Hall-bar devices of g) tetragonal and h) hexagonal FeTe nanoplates, respectively. i,j) Relationship between RS and
temperature of i) tetragonal and j) hexagonal FeTe devices, respectively. k) Relationship between Rxy and temperature of 32 nm tetragonal and 30 nm hex-
agonal FeTe nanoplates. l) Temperature-dependent AHE of the 30 nm hexagonal FeTe. Reproduced with permission.[88] Copyright 2020, Springer Nature.

opportunities in various applications including oscillators, an ionic field-effect transistor to modulate the energetics of
ultrafast memories, and logic circuits.[254,255] There are some the CDW phases and dramatically modulate the electronic
straightforward methods to characterize the CDW order or TCDW properties of the 1T-TaS2 nanosheet by controlling Li ion inter-
in 2D m-TMDs including temperature-dependent resistivity calation. Meanwhile, a well-ordered CDW state with a 2 × 2
measurement, scanning tunneling microscopy, low-tempera- superstructure was clearly observed on the sub-10 nm 1T-TiSe2
ture transmission electron microscope (TEM), and tempera- nanosheet by scanning tunneling microscope (STM) at ≈77 K
ture-dependent Raman spectroscopy. For example, Zhang et (Figure 16c).[182] The TEM analysis were used to directly visu-
al. have been reported the CDW order of 1T-TaS2 nanosheets alize the periodic lattice distortion of the 2H-TaSe2 monolayer
with the decrease of the thickness measured by temperature- film (Figure 16d), the orientation of 3 × 3 CDW superstructure
dependent resistivity.[256] In Figure 16a, with decreasing thick- can be observed in the 2H-TaSe2 monolayer at 80 K.[113] In addi-
ness of 1T-TaS2 nanosheets, the phase transitions temperatures tion, variable-temperature Raman characterizations are estab-
of incommensurate CDW (ICCDW) and nearly commensurate lished to detect the TCDW of 2H-TaSe2 with thickness of ≈0.8,
CDW (NCCDW) decrease and then suddenly vanish at the ≈2.8, and ≈50 nm at different temperatures (Figure 16e). Note
thicknesses of ≈10 and ≈3 nm, respectively.[256] The tempera- that, as the temperature of 2H-TaSe2 monolayer decreases, the
ture-dependent resistivity measurement can also be applied E2g mode begins to move to high wave number owing to the
to other m-TMDs such as 1T-VS2,[193] 3R-TaSe2,[37] 1T-VSe2,[257] phonon hardening until the temperature is below ≈125 K, and
and 1T-TiSe2[258] with varying thicknesses. Figure 16b describes then E2g shifts to a low wave number with further decreasing

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Figure 16. The CDW phase in m-TMDs. a) The relationship between electrical resistivity and temperature based on 1T-TaS2 nanosheets. b) The ionic
field-effect transistor based on 1T-TaS2 nanosheet. Reproduced with permission.[256] Copyright 2015, Springer Nature. c) The atomic-resolution STM
images based on 1T-TiSe2 nanosheet. Reproduced with permission.[182] Copyright 2016, American Chemical Society. d) The TEM image based on 2H-TaSe2
monolayer. e) The Raman spectroscopy characterizations based on 2H-TaSe2 nanosheets. Reproduced with permission.[113] Copyright 2018, Wiley-VCH.

temperature. In this way, the TCDW of 125 K was determined lenges the above point.[261] The mechanism of van Hove singu-
for the monolayer 2H-TaSe2. As the thickness of the 2H-TaSe2 larity was subsequently used to understand the CDW order in
nanosheets decrease from ≈50 to ≈0.8 nm, the TCDW signifi- NbSe2.[27] However, the NbSe2 monolayer exhibited a contro-
cantly increase from ≈90 to ≈125 K.[113] Such Raman characteri- versial result in electric transport measurement.[199] In general,
zations are also applied in other m-TMDs including 1T-TiSe2,[24] the mechanisms of Fermi surface nesting and van Hove sin-
2H-NbSe2,[198] 1T-TaSe2,[259] and so on. But, the possible mecha- gularity were more suitable for explaining the CDW order in
nism of CDW order in m-TMDs is controversial. G. GrÜner different systems (e.g., 1D system). In recent years, the origin
first proposed the Fermi surface nesting mechanism in 1988.[260] of CDW order in 2D m-TMDs was reasonably revealed by the
But, the origin of the CDW order of the 2H-NbSe2 bulk chal- mechanism of electron-phonon coupling was proposed.[27,113]

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When the energy difference of the electron state is smaller than Meanwhile, in Figure 17d, Coronado et al. exhibited that the TSC
that of phonon energy, the interaction between the electron and increased from 0.5 to 2.2 K when the layer thickness of 2H-TaS2
the phonon is significant. When the interaction of the elec- decreased from bulk to 3.5 nm.[268] Moreover, Liu et al. reported
tron and the phonon exceeds the repulsive shielding repulsive the SC TSC of TaSe2 was increased from 0.2 to1.6 K by switching
screened Coulomb interaction, it is beneficial to form a SC/ the phase from 2H to 3R (Figure 17e).[37]
CDW phase. On the other hand, the changes in CDW order Several methods have been employed to improve TSC of 2D
based on thickness in m-TMDs remain controversial. m-TMDs including interface effects, high pressure, chemical
What’s more, the thickness-depended CDW of the same doping, and so on.[259,260,262] For example, Jia et al. reported that
m-TMDs has a totally contrary result. For instance, Mak et al. the single-layer FeSe nanosheets grown on Nb-doped SrTiO3
demonstrated that as the thickness of exfoliated NbSe2 reduced (001) substrates show superconductivity at temperatures as
from bulk to single-layer, the TCDW could be enhanced from high as 109 K, owing to interface-enhanced electron–phonon
36 ± 1 to 145 ± 3 K,[198] which indicate that as the thickness of coupling.[269] Sipos et al. reported that the superconductivity of
NbSe2 decreases, the CDW order is strongly enhanced. But, 1T-TaS2 first appears in the NCCDW state, remains roughly at
Crommie et al. reported that compare to TCDW = 33 K in bulk 5 K by applying 3–25 GPa pressure, and survives to very high
NbSe2, the TCDW of NbSe2 monolayer film synthesized on epi- pressures, which may be attributed to the fact that pressure
taxial bilayer graphene reduced to ≈25 K, which present that can affect the electronic interactions of the m-TMDs without
as the thickness of NbSe2 decreases, the CDW order is signifi- increasing the degree of internal disorder.[237] Meanwhile, Li
cantly suppressed.[199] The diverse results may be attributed to et al. discovered superconductivity of WTe2 with a TSC of ≈2.6 K
differences in the substrates or experimental conditions. by intercalating potassium (K) into the vdW gap of type-II Weyl
semimetal WTe2, in which superconductivity was promoted
purely by electron doping effect, without a considerable lattice
4.3. Superconductivity in 2D m-TMDs change.[270]

Superconductivity is the phenomenon of electron correlation

in Bardeen–Cooper–Schrieffer SC theory. In many cases, the 5. Applications of 2D m-TMDs
development of novel states of matter has been promoted by
exploring the coexistence between superconductivity and other 5.1. High-Performance Electronic Devices
collective electronic states. 2D SC materials have become a hot
topic owing to their fantastic physical properties and a broad Several 2D m-TMDs including 2D 1T-TiSe2, 1T-TaS2, and
range of applications in many fields such as topological super- 1T-TaSe2 exhibit the CDW phase transitions, which can be used
conductor and quantum computation. There are many intrinsic to construct high-performance electronic devices, such as elec-
superconductors in 2D m-TMDs such as 2D 1T-TiSe2, 1T-TaS2, trical oscillators,[271] nonvolatile memory storage devices,[272] and
2H-TaS2, 2H-NbSe2, 3R-TaSe2, and so on.[37,77,201,262–268] highly sensitive room temperature bolometers.[113] The phase
In Figure 17a, the temperature-dependent scanning tun- transitions of 2D m-TMDs caused by lattice reconstruction lead
neling spectroscopy (STS) results reveal that when the tempera- to modifications of the electrical properties. Thus, the metal-to-
ture is below ≈2.8 K, the superconductivity has been found in insulator transition (MIT) and the insulator-to-metal transition
2H-TaS2.[265] However, the characterization of the superconduc- (IMT) in 2D m-TMDs have attracted more and more attention.
tivity of 2D m-TMDs with STM/STS requires a conducting sub- With mutual transition between different phases (commen-
strate. Moreover, the influence of the substrate and the interface surate CDW (CCDW), ICCDW, and NCCDW), MIT and IMT
(between material and substrate) on the SC properties are hard can be modified by the thickness, the ambient pressure, inter-
to rule out. The electrical transport measurement is another calation, doping, and the applied electric source–drain or gate
more direct and effective method to study the superconduc- bias.[255,262,272] Balandin et al. reported the integrated 1T TaS2-
tivity of 2D m-TMDs. For example, Liu et al. reported the thick- BN-graphene voltage-controlled oscillator (VCO), in which the
ness-dependent SC property of the 2H-NbSe2 (grown by CVD) TaS2 was protected by h-BN nanosheets to prevent oxidation
through fabricating Hall-bar devices (Figure 17b).[77] And Hunt and preserve the CDW phase, and the current density and load
et al. reported the thickness-dependent superconductivity of the resistance of the transistor constructed by graphene match very
2H-TaS2 and 2H-NbSe2 (obtained by exfoliated) through fabri- well with TaS2.[255] The operating mechanism of 1T TaS2-BN-gra-
cating several multiterminal transport devices (Figure 17c).[264] phene VCO was the conversion of IMT and MIT related to the
The exploration of SC in m-TMDs with high transition temper- phase transition of the NCCDW and ICCDW phases in 1T-TaS2.
atures remains a critical challenge in the scientific and material These oscillators without a complicated biasing circuit can
fields. Superconductivity is affected by some structure parame- operate at the temperature up to ≈320 K, which can be applied to
ters of 2D m-TMDs such as layer thickness and phase transition. communication systems and other systems as a kind of inexpen-
In Figuer 16b, Liu et al. reported that as the thickness of as-grown sive technology. So far, the functions of most computer storage
NbSe2 increase from monolayer to 10-layer, the transition tem- elements are based on the multi-stability of the device, which
perature of superconductivity (TSC) increase from 1.0 to 4.56 K. was driven by the local manipulation of electron density in tran-
In Figure 17c, Hunt et al. demonstrated that the critical TSC sistors or switching of magnetic or ferroelectric order.[273] More-
of 2H-NbSe2 was reduced with decreasing the layer thickness. over, the another possible mechanism is the transition between
However, the opposite trend was observed in 2H-TaS2, in which IMT and MIT by the motion of ions. Mihailovic et al. reported
the TSC was increased with decreasing the layer numbers.[264] ultrafast non-volatile resistance switch of the CDW systems, in

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Figure 17. Superconductivity of 2D m-TMDs. a) STS results based on 2H-TaS2 nanosheet. Reproduced with permission.[265] Copyright 2014, American
Physical Society. b) Relationship of longitudinal resistance Rxx and temperature based on 2H-NbSe2 device. Reproduced with permission.[77] Copyright 2017,
Springer Nature. c) Superconductivity of atomically thin 2H-TaS2 and 2H-NbSe2 in zero magnetic field. Reproduced with permission.[264] Copyright 2018,
Springer Nature. d) 2D superconductivity and enhanced TSC in atomically thin 2H-TaS2. Reproduced with permission.[268] Copyright 2016, Springer Nature.
e) Comparison of TC reported in 1T- 2H- and 3R-TaSe2. Reproduced with permission.[37] Copyright 2020, American Chemical Society.

which the 50–100 nm 1T-TaS2 nanosheets were converted from with a high response (up to 2.6 × 103 V (W mm−2)−1),[112] which
an insulator to metal at a low temperature by injecting a short depends on the conversion of NCCDW and ICCDW in 1T-TaS2
pulse current and then the charge formed a domain wall by cou- nanosheets, exhibiting an extremely high-temperature coeffi-
pling to gradients of the CDW order parameter.[254] The mecha- cient of resistance (TCR) up to −33% K−1. The high conductivity
nism is that when the charge pulse passes through the 1-TaS2 of 1T-TaS2 films is also beneficial for bolometric application,
channel, there are a transition from commensurately ordered because Johnson dark noise can be reduced by higher con-
polaronic Mott insulating state to a metastable electronic state ductivity. The 1T-TaS2 bolometers can operate at a wide range
with textured domain walls, accompanied by a conversion of of environmental temperatures, owing to the phase transition
polarons to band states, which open up new avenues for manip- temperature of NCCDW-ICCDW in 1T-TaS2 above the room
ulating all electronic states in non-volatile memory devices. temperature. Furthermore, the 1T-TaS2 bolometric performance
In addition, Xie et al. demonstrated 1T-TaS2 films bolometer can be optimized by doping metal atoms including Ti and Hf

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or modulate the phase transition temperature of NCCDW– To better understand the adsorption behavior of H* on TMDs,
ICCDW. Additionally, in the field of the transistors, diodes, and Yakobson et al. reported the electronic structure of H* inter-
other circuit elements, the replacement of s-TMDs by m-TMDs mediates. The position of the lowest unoccupied state (εLUS)
will bring many potential advantages such as the enhance- determines the adsorption strength of H* on the surface of
ment of inherent radiation hardness and low cost. For example, TMDs, which can be used as the basis for selecting a planar
Balandin et al. reported all metal electrically gated switches and active TMD electrocatalyst (Figure 18a).[280] In Figure 18b, the
logic circuits of 2H-TaSe2 films,[274] in which the devices based relatively low εLUS (<–5.8 eV) have been found in the group
on 2H-TaSe2 thin-film can be used as electrically gated devices V TMDs (H-VS2, H-TaS2, and H-NbS2), which indicates
with strongly non-linear current–voltage characteristics. The that m-TMDs are more suitable high-efficiency HER cata-
drain–source current in this device presents sudden change lysts. To our knowledge, 1T-VS2,[104,281] 1T-VSe2,[50] H-NbS2,[280]
from a high-resistance to a conductive state, and the threshold 1T-TaS2,[111,160] 2H-TaS2,[55,111] 1T-NiTe2,[130] etc., have been
can be adjusted by the gate voltage. studied as HER catalyst. For example, Zhang et al. reported the
metallic 2H-TaS2 nanosheets have been found to be an efficient
electrocatalyst for the HER (Figure 18c–e).[55,111] The Tafel slopes
5.2. Electrocatalysis of 2H-TaS2/Au were calculated to be 33–42 mV dec−1, which
is even equivalent to the value of Pt (≈31 mV dec−1), because
Electrocatalysis is the heart of clean energy conversion in future its abundant active sites concentrated on the edges and basal-
technologies including fuel cells, metal-air batteries, photocata- planes (Figure 18d). In Figure 18e, the higher electrocatalytic
lytic conversion devices, CO2 electro-chemical reduction, etc. activity of 2H-TaS2 nanosheets is significantly higher than
Benefitting from the intriguing structural, electronic properties its initial state after 5000 cycles, because the surface oxide of
and other intrinsic features, 2D materials have received wide- 2H-TaS2 can be stripped by hydrogen bubbles, which reflects its
spread attention in electrocatalysis such as HER, oxygen reduc- inherent electrocatalytic activity. Moreover, Zhang et al. demon-
tion reaction (ORR), hydrogen oxidation reaction (HOR), oxygen strated that the 1T-NiTe2 exhibited high electrocatalytic activity
evolution reaction (OER).[275,276] Generally speaking, graphene is in pH-universal HER.[130]
a forthcoming choice as an ORR catalyst, layered double hydrox- Many methods have been applied to improve the catalytic
ides and associated oxides are good catalysts for OER while 2D activity of m-TMDs, such as defects, phase transitions, etc. For
TMDs are suitable as an intrinsic HER electrocatalyst.[276] As instance, Chen et al. introduced high-density atomic-scale pores
sustainable energy development receives global attention, it is into 1T-TaS2 through oxygen plasma, resulting in a large number
very important to assess the effectiveness of 2D TMDs in these of defects that can be used as catalytic active sites, thereby
areas. The potential advantages of 2D TMDs in the field of elec- improving HER efficiency. (Figure 18f).[160] In Figure 18g,h, as
trocatalysis can be summarized in three aspects:[277] I) large spe- exposure time of 1T-TaS2 nanosheets by oxygen plasma prolongs
cific surface area can provide a high density of surface active from 0 to 5, 10, and 15 min, the onset potential of HER decreases
sites; II) excellent mechanical properties can provide catalytic from 310 mV of the pristine nanosheets to 302, 200, and 225 mV.
durability; III) strong conductivity (thermal and electrical) can 1T-TaS2 nanosheets exhibit the best catalytic activity with a cur-
assist thermal diffusion during reactions. Thus, compared to rent density of 10 mA cm−2 at 564 mV and very low TaS2 loading
bulk materials, 2D TMDs nanosheets have better catalytic sta- of 0.24 mg cm−2 after being exposed to oxygen plasma for
bility and catalytic activity, which are also excellent building 10 min, which indicates that the HER activities of the 1T-TaS2
blocks for constructing hierarchical composite catalysts. nanosheets are significantly improved by plasma treatment. In
However, the conductivity of s-TMDs is relatively low, and addition, Zhang et al. reported that compared to metallic 1T-TaS2,
the limited active sites are focused only on the edges, which metallic 2H-TaS2 has better electrocatalytic HER performance
limits their catalytic performance.[278] Various methods such as (Figure 18i,j).[111] The hydrogen adsorption free energy (ΔGH)
phase change or introduction of a suitable conductive substrate value of the 2H-TaS2 (0.23 eV) is lower than that of 1T-TaS2
were used to improve the conductivity of s-TMDs. The insta- (0.91 eV) by DFT calculation (Figure 18i). The overpotential value
bility of 1T-phase TMDs produced by phase change and the of and Tafel slope of 2H-TaS2 (≈113 mV and ≈50 mV dec−1) is
complexity of constructing s-TMDs on conductive substrates better that of 1T-TaS2 (≈249 mV and ≈75 mV dec−1), which
severely hinder their practical application.[27] To solve the above suggests that the HER performance of TaS2 nanosheets can be
problems, Zhang et al. reported a post-treatment of the powder optimized to a ideal value through changing the phase state.
precursor then followed by CVT robust method to prepare
1T′-MoS2, which shows more excellent HER performance and
better charge transport ability compare to 2H-MoS2.[279] More- 5.3. Metal Electrode Contacts
over, in all TMDs, m-TMDs present superior performance for
electrocatalysis due to the drastic reduction of charge transfer The emerging 2D layered semiconductors including TMDs
resistance in the metallic phase. And then, we review the state- have potential applications in advanced electrical and optoelec-
of-the-art of m-TMDs as electrocatalysts in the field of electro- trical devices with increased functionality, performance, and
catalytic reactions. The key factor determining the ratio of HER integrated circuit scaling. Therefore, a lot of efforts have been
follows the Sabatier principle: the balance between adsorption carried out to fabricate field effect transistor (FET) devices with
and desorption. The relative adsorption free energy of H* inter- good performance, for example, metal-semiconductor contact
mediates as a criterion for evaluating catalyst activity and is with band-alignments could be readily constructed by a typ-
widely used to determine suitable HER candidate catalysts.[280] ical lithography approach. However, some issues still remain

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Figure 18. The applications of m-TMDs in electrocatalysis. a) Schematic illustration of the MX2 DOS. b), Theoretical value of the εLUS for MX2. Repro-
duced with permission.[280] Copyright 2017, Springer Nature. c) Schematic diagram of the HER process of 2H-TaS2/Au foils. d) The Tafel plots of the
various materials. e) Polarization curves (iR-corrected) of 150 nm 2H-TaS2 before and after 5000 cycles. Reproduced with permission.[55] Copyright 2017,
Springer Nature. f) Schematic illustration of HER of TaS2 after being treated by plasma. g) The relationship between the time of oxygen plasma treat-
ment and defect density. h) Polarization curves and derivative polarization curves of TaS2 nanosheets treated by plasma at 0.24 mg cm−2. Reproduced
with permission.[160] Copyright 2016, Wiley-VCH. i) ∆GH diagram of the different H adsorption states. j) Polarization curves and Tafel plots of 2H, and
1T-TaS2 on Au foils, and Pt, respectively. Reproduced with permission.[111] Copyright 2018, Wiley-VCH.

unresolved in conventional metals contacted 2D s-TMDs: first, and disorder, thereby, the formation of the glassy layer caused
it is difficult to form strong interface bonds between the metals by interdiffusion and strain.[181] Third, in a high-energy metal
and the 2D s-TMDs owing to no dangling bonds on the pristine deposition process, the crystal lattice at or near the interface of
surface of a 2D material, thereby increase the contact resist- the 2D s-TMDs is destroyed by atomic or cluster bombardment
ance and cause Fermi-level pinning.[107,129] Second, chemical and strong local heating.[23] The performance of electronic and
bonding as well as diffusion between the metal and the 2D optoelectronic devices is deeply affected by the electrical contact
s-TMDs leads to the formation of considerable defects, strain, between the semiconductor and the external circuit. So, it is

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Figure 19. The 2D m-TMDs used as metal electrode contacts for 2D s-TMDs. The schematic model of a) m-TMD/s-TMD vertical heterostructure and
b) m-TMD/s-TMD lateral heterostructure FETs. Reproduced with permission.[107,178] Copyright 2019, Wiley-VCH; Copyright 2018, American Chemical
Society. c) Band profiles of the VSe2/WSe2 and VSe2/MoSe2 vertical heterostructure. Reproduced with permission.[174] Copyright 2019, American Chem-
ical Society. d) OM image of VSe2/WSe2 vdWHs FETs arrays. e) Output and f) transfer characteristics of bilayer WSe2 FETs (on 70 nm SiNx/Si substrate)
with VSe2 nanoplates as contacts. g) The cumulative distribution of two-terminal mobility values of WSe2 FETs with VSe2 nanoplates deposited metal
as contacts. Reproduced with permission.[154] Copyright 2020, Springer Nature. h) OM image of the 1T′-MoTe2//2H-MoTe2 lateral heterostructures FETs
devices array. i) Output characteristics of representative 2H-MoTe2 FETs with 1T′-MoTe2 contact and Pd/Au metal contact, respectively. j) The mobili-
ties of 2H-MoTe2 with 1T′-MoTe2 as contact for different channel length. k) Output characteristics of the 1T′-MoTe2/2H-MoTe2 lateral heterostructure
photodetector under 1064 nm laser illumination. Reproduced with permission.[181] Copyright 2019, American Chemical Society.

urgent to choose electrode metals with ideal working functions Zhang et al. reported vertically stacked metal-semiconductor
and proper fabricating process to reduce the Schottky barrier, TMDs vdWHs, in which Schottky-diode or Ohmic contact-type
Fermi-level pinning, and other uncontrollable factors. band alignments could be formed between VSe2 and p-type
As far as we know, 2D m-TMDs have high electrical con- WSe2 or n-type MoSe2, respectively (Figure 19c).[174] And then,
ductivity comparable to the traditional metals, which makes Zhang et al. presented that the mobility of 1T VTe2-contacted
them an excellent electrode for fabricating the FET device. For MoS2 monolayer devices is ≈47.5 cm2 V−1 s−1, which is 6 times
m-TMDs/s-TMDs vertical heterostructures, the 2D m-TMDs higher than that of Ti/Au-contacted MoS2 monolayer devices
as in situ vdW epitaxial metal electrode contacts can guarantee (≈8.1 cm2 V−1 s−1). Moreover, Duan et al. showed that the VSe2
atomically sharp interfaces owing to the absence of direct chem- nanosheets contacted-WSe2 bilayer demonstrate excellent device
ical bonding or surface reconstructions. For m-TMDs/s-TMDs performance (Figure 19d–g).[154] Figure 19e,f show a high on-cur-
lateral heterostructurs with atomically sharp and seamless rent density up to 900 µA µm−1 and an on/off ratio of over 107 of
across coplanar interfaces, the coplanar m-TMDs contacts offer a WSe2 bilayer FET with VSe2 nanosheets used as metal electrode
low-barrier 1D interface to the s-TMDs, allowing current injected contacts. The cumulative mobility distribution of the bilayer
from m-TMDs to s-TMDs. A lot of efforts have been done to WSe2 FET with VSe2 nanosheets used as contacts (Figure 19g)
design the 2D metal-semiconductor contact including m-TMDs/ shows a much narrower distribution than that with deposited
s-TMDs vertical heterostructures (Figure 19a) and m-TMD/s- metal contacts.
TMD lateral heterostructures (Figure 19b) to reduce surface On the other hand, m-TMDs/s-TMDs lateral heterostruc-
defect, Fermi level pinning effect, and enhance the performance tures have also made outstanding contributions to enhance the
of m-TMDs FETs.[107,178] Recently, Duan et al. reported that the performance of semiconductor devices. For instance, Kong et
WSe2 FET with NbTe2 and NiSe used as metal electrode contacts al. reported that compared to traditional nickel contacted-MoS2
(form vertical vdWH with WSe2) show better on-state current monolayer FET, the mobility of MoS2 monolayer FET with lat-
and mobilities than FET with traditional Cr/Au electrodes.[107,129] eral 2D VS2 contact has been improved by 6-fold.[178] Moreover,

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Dai et al. reported large-scale integrated 2H MoTe2 FETs with m-TMDs have been applied to the fields of oscillators, bolometers,
coplanar metallic 1T′-MoTe2 as contacts obtained by phase engi- and nonvolatile memory devices. And then, m-TMDs have been
neering approaches (Figure 19h–k).[181] Figure 19h shows large- considered having great development potential for electrocatalysis
scale 1T′-MoTe2/2H-MoTe2 lateral heterostructure FETs array, owing to the large specific surface area, mechanical properties,
in which metallic 1T′-MoTe2 is used as contacts. The current of and strong conductivity. Moreover, 2D m-TMDs can be used as in
coplanar metallic 1T′-MoTe2 contacted 2H-MoTe2 FETs is one situ vdW epitaxial metal electrode contacts to improve the interface
order of magnitude larger than that of conventional Pd/Au and reduce the contact resistance, thereby further promote the
metal contacted 2H-MoTe2 FETs (Figure 19i). In Figure 19j, electrical and optoelectronic properties of s-TMDs.
the average field effect mobility of coplanar metallic 1T′-MoTe2 In the past several years, although considerable progress
contacted 2H-MoTe2 FETs is 20–24 cm2 V−1 s−1. Figure 19k dem- has been made in m-TMDs, there are still many challenges
onstrates that coplanar 1T′-MoTe2 contacted 2H-MoTe2 FETs and limits at the current stage. I) The synthesis of few-layers
show the high photoresponsivity of ≈1.02 A W−1 under 1064 nm or monolayer m-TMDs with preferred structures remain chal-
laser illumination. Moreover, the 2D lateral metal-semicon- lenging because of the structural diversity. Therefore, more
ductor can also be formed by post-treatments including laser methods need to be developed to controllably synthesize the
irradiation,[33] e-beam irradiation,[143] Li intercalation,[146] argon specific phases of 2D m-TMDs. II) The synthesis decides the
plasma,[177] etc., to effectively enhance the electrical properties applications of materials, however, the synthetic method of
of 2D s-TMDs. For instance, Jo et al. presented that the mobility 2D m-TMDs is still in its infancy, which is far lagging behind
of 1T′-MoTe2 coplanar contacted few-layer 2H-MoTe2 is 4-fold the fundamental material research and device demonstra-
and 133-fold than that of Au contacted 2H-MoTe2 at 300 and tion. Although the novel salt-assisted CVD can be applied in
77 K, respectively.[71] Meantime, they found an ultralow contact the research of m-TMDs to lower the melting point of metal
barrier height of ≈25 meV, which directly contributes to the oxides and increase the size of m-TMDs, the size and yield of
1T′/2H-MoTe2 coplanar contacted FETs outperforming conven- 2D m-TMDs are still small which restricts its practical applica-
tional top-contacted FETs. tions. Therefore, it is urgent to study the fundamental mecha-
The m-TMDs as contacts can improve the interface and reduce nism of the CVD growth methods and develop new synthetic
the contact resistance, thereby further improving the electrical methods to promote the preparation of wafer-scale m-TMDs
and optoelectronic properties of s-TMDs. However, these per- single crystals and further promote the practical applications
formances are still far from practical application requirements. of m-TMDs. In addition, these heterostructures provide a reli-
We need to improve the integration technology continuously to able platform for studying new interlayer coupling between
realize the practical application of 2D materials truly. different materials and offer multiple physical properties to
satisfy different application requirements, but, the types of
heterostructure of 2D m-TMDs are still few. So, the new types
6. Conclusions and Perspective of heterostructure based on 2D m-TMDs need to be developed.
Lastly, many 2D m-TMDs often can be easily oxidized under
In conclusion, we have summarized the state-of-the-art of 2D ambient conditions or during synthesis process, which hinder
m-TMDs including metallic and semimetallic 2D TMDs, focusing their practical applications. The integrated air-free vacuum
on their structures, synthetic methods, key properties, and poten- systems including material synthesis, characterization, device
tial applications. First, we have reviewed the basic H and T struc- fabrication, and measurements, must be taken to avoid sur-
tures of 2D m-TMDs and their extended structures such as 1T, face oxidation. III) The controversies and dimness about the
1T′, 1Td, 2H, and 3R, and carefully analyzed the connections and existence of magnetism, mechanisms of the origin of CDW
differences between different crystal structures. Subsequently, we order, thickness-dependent CDW phase transitions, and the
have reviewed the controllability of the key CVD growth methods interplay between CDW and superconductivity in the 2D limit
of 2D m-TMDs single crystal for controlling the number of of m-TMDs are still unresolved. Therefore, further theoretical
layers, phases, lateral sizes, orientation, defects and doping of 2D and experimental work is required. IV) Although some prac-
m-TMDs, as well as the synthesis of m-TMDs/s-TMDs vertical tical applications of m-TMDs have been discussed, the direct
vdWHs and m-TMDs/s-TMDs lateral heterostructures. Moreover, relationship between the physical properties and applications
other growth methods of 2D m-TMDs including mechanical is still unclear. Thus, wider applications in the field of elec-
exfoliation, chemical exfoliation, MBE, hydrothermal method, tronics, optoelectronics, spintronics, and higher performance
salt-templating synthesis, topochemical transformation, and the devices using m-TMDs need to be explored. Although it is very
method of phase transition from semiconductor to metal by post- challenging, we believe researchers will resolve these prob-
treatments have been presented. And then, we have further sum- lems shortly because 2D m-TMDs materials exhibit countless
marized the attractive physical properties of m-TMDs including fascinating futures, not only for the purely scientific field but
intrinsic magnetism, CDW order and superconductivity, as well also in practical applications in various fields.
as their respective characterization methods. In particular, the pos-
sible mechanisms of CDW order, the thickness-dependent CDW
phase transitions, some factors affecting the superconductivity, Acknowledgements
and methods to enhance the superconductivity have been care-
This work was supported by National Natural Science Foundation of
fully analyzed. Finally, we have discussed the versatile applica-
China (No. 51872086), the Hunan Key Laboratory of Two-Dimensional
tions of m-TMDs including high-performance electronic devices, Materials (Grant No. 2018TP1010), and the Innovative Research Groups
electrocatalysis, and metal electrode contacts. Recently, the 2D of Hunan Province (Grant 2020JJ1001).

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Bei Zhao received her B.S. degree in Material Chemistry from the Shandong University of
Technology at 2014, her M.A. degree in Applied Chemistry from Southwest University at 2017, and
her Ph.D. degree in Physical Chemistry from Hunan University at 2021. Her research is focused on
controllable synthesis of 2D materials and their applications in electronics, and optoelectronics.

Xidong Duan received his B.S. degree in Chemistry from Hunan University in 1993, his
M.A. degree in Materials from Hunan University in 1996, and his Ph.D. degree in Chemistry
from Hunan University in 2016. Afterward, he joined the College of Chemistry and Chemical
Engineering, Hunan University, China, as a professor. His current research interests include 2D
materials, heterostructures, and their applications.

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